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The 18th ICIT Conference PROGRESS IN CRYOGENICS AND ISOTOPES SEPARATION
Calimanesti-Caciulata, Romania October 25-26, 2012
Tehnoredactare: Camelia Asprita Coperta: Camelia Asprita ISBN: 978-973-750-228-5
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CONTENTS
Plenary Lectures
1. ECOSYSTEM OF INNOVATIONS IN NANOTECHNOLOGIES FOR SAFETY, SECURITY AND SUSTAINABILITY Ashok Vaseashta 2. DETERMINATION OF TRITIUM BY ELECTROLYTIC ENRICHMENT IN ACCREDITED LABORATORY Jasmina Koar Logar, Denis Glavi Cindro 3. NITRIDE NUCLEAR FUELS Damian Axente 4. ISOTOPE TRANSIENT METHODOLOGY FOR CATALYSED SURFACE REACTION ANALYSIS Mihai Varlam 5. RESERVED TITLE Liviu Stefan
SECTION 1: Stable Isotopes Physics. Technologies and Applications

1. EXPERIMENTAL EVIDENCES OF THE INFLUENCE OF NITROGEN GAS ON THE TRIMER IONS IN LOW RESOLUTION MASS SPECTROMETRY OF HYDROGEN ISOTOPES N. Bidic, G. Bulubaa 2. THE ACCURACY OF FOURIER TRANSFORM INFRARED SPECTROSCOPY METHOD USED TO QUANTIFY THE DEUTERIUM CONCENTRATION IN HEAVY WATER STANDARDS Gabriela Raducan, Iuliana Piciorea, Ioan Stefanescu
SECTION 2: Cryogenics Technologies and Equipments

1. THERMAL AND MAGNETIC DESIGN OF A HTS HIGH MAGNETIC FIELD GENERATOR USING SUPERCONDUCTING HELMHOLTZ COILS Ion Dobrin, Alexandru Morega, Adrian Nedelcu, Mihaela Morega, Dan Daniel 2. IMPORTANCE OF LOCAL LEAK RATE IN DETERMINATION OF GAS LEAK LOCALIZATION IN ENCLOSED INDUSTRIAL BUILDING Stefan-Ionut Spiridon, Sorin Gherghinescu, Gheorghe Popescu
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3. PRESSURE LOSS DETECTION IN PLANTS WITH CONTINUOUS MONITORING BY MEASURING THE FLOW PARAMETERS Sorin Gherghinescu, Stefan-Ionut Spiridon, Gheorghe Popescu 4. EXPERIMENTAL DETERMINATION OF FLOW PARAMETERS VARIATION TO LOCATE ANY MALFUNCTIONS FOR CONTINUOUS MONITORING INSTALLATIONS Sorin Gherghinescu, Ionu Spiridon, Gheorghe Popescu, Marian Vacaru 5. HIGH QUALITY PURIFICATION OF DEUTERIUM FOR CRYOGENIC DISTILLATION SYSTEM FROM CTRF PROJECT Florina Porcariu, Mirela Drghia, Gheorghe Pasca 6. DETERMINATION OF LOCAL LEAK RATE AND GAS LEAK LOCALIZATION IN INDUSTRIAL BUILDING Stefan-Ionut Spiridon, Sorin Gherghinescu, Gheorghe Popescu, Marian Vacaru 7. SOLUTII DE CONTROL UTILIZATE IN PROCESECRIOGENICE CU APLICATIE LA PILOTUL EXPERIMENTAL DE LA RM. VALCEA Sorin Brotac, Alexandrina Dragoi, Lucian Radu, Sabin Chivescu
SECTION 3: Science and Materials Engineering

1. SPIN DYNAMICS EVIDENCED BY EPR IN Sn1-xMnxO2 NANOPARTICLES ANNEALED AT DIFFERENT TEMPERATURES A. Popa, D. Toloman, O. Raita, M. Stan, B. S. Vasile, L. M. Giurgiu 2. EVIDENCE BY EPR OF FERROMAGNETIC PHASE IN Mn-DOPED ZnO NANOPARTICLES ANNEALED AT DIFFERENT TEMPERATURES D. Toloman, A. Mezaros, A. Popa, O. Raita, T. D. Silipas, B. S. Vasile, A. R. Biris and L. M. Giurgiu 3. MAGNETIC RESONANCE INVESTIGATION OF Co2+ IONS IN ZnO NANOPOWDERS M. Stan, A. Popa, D. Toloman, O. Raita, A. R. Biris, Ghe. Borodi, A. S. Biris, L. M. Giurgiu 4. Zn1-xFexO POWDERS AS SEEN BY EPR O. Raita, A. Popa, D. Toloman, M. Stan and L. M. Giurgiu 5. HYBRID MATERIALS OBTAINED BY NICKEL IMMOBILIZATION ON MESOPOROUS MCM-41 AND THEIR APPLICATION IN ALCOHOLS OXIDATION Violeta Niculescu, Ramona Ene, Ionut Iordache, Viorica Parvulescu 6. EXPERIMENTAL RESULTS ON CHEMICAL CLEANING OF FILMED SA106 STEEL L. Popa, M. Tunaru, L. Velciu 7. EVALUATION OF PHISICAL STABILITY OF THE U-ZrH SYSTEM Mariea Gruia (Deaconu), Ion Ciuca, Marioara Abrudeanu, Tiberiu Meleg, Iulia Dumitrescu 8. BEHAVIOUR EVALUATION OF SOME STRUCTURAL MATERIALS FOR HEAVY WATER PLANT EXPOSED TO SULPHURETTED HYDROGEN ENVIRONMENT Lucian Velciu, Maria Mihalache, Al. Niu, Laureniu Popa, Alice Dinu
9. INVESTIGATED OF TUNGSTEN-LEAD-BORATE GLASSES BEFORE AND AFTER LASER IRRADIATION M. Rada, E. Culea, N. Aldea, S. Rada, V. Rednic, A. Bot, D. Silipas 10. PLATINUM BASED MULTI-SHELL MAGNETIC NANOPARTICLES AND FUNCTIONALIZED COMPOSITES O. Pana, C. Bele, S. C. Matea, M. L. Soran, C. Leostean, M. Stefan, S. Macavei 11. GLYCEROL HYDROGENOLYSIS OF GLYCEROL TO PROPYLENE GLYCOL ON COMMERCIAL NICKEL CATALYSTS DESCRIBED BY A MATHEMATICAL MODEL Adriana Marinoiu, Elena Carcadea, Catalin Capris, Claudia Cobzaru, Vasile Tanislav, Iordache Ioan 12. EFFECT OF DISPERSION SOLVENT IN CATALYST INK FOR MEMBRANE ELECTRODE ASSEMBLIES Adriana Marinoiu, Irina Petreanu, Laurentiu Patularu, Mircea Raceanu, Amalia Soare
SECTION 4: Nuclear Power - fission and fusion

1. GENERATION IV NUCLEAR ENERGY SYSTEMS OVERVIEW Ramona-Maria Voiculescu, Viorica-Maria Nistor, Marius Olteanu 2. V-4Cr-4Ti ALLOY-A PROMISING CORE CLADDING MATERIAL FOR GEN IV REACTORS D. Ohai 3. INR EXPERIMENTAL CONTRIBUTIONS TO THE FP7- STYLE PROJECT Maria Roth, Vasile Piigoi, Maria Mihalache, Ionut Niu 4. INR CONTRIBUTION TO THE FP 7 STYLE PROJECT AS CONCERNING LBB CONCEPT Vasile Radu 5. UNSATURATED HYDRAULICS AND CONTAMINANT TRANSPORT SIMPLE TEST MODEL FOR ALLIANCES AND FEHM BENCHMARK Alina Constantin, Daniela Diaconu, Alain Genty 6. MICROSTRUCTURAL CHARACTERIZATION OF OXIDE LAYERS FORMED ON CARBON STEELS IN SECONDARY CIRCUIT CONDITIONS OF CANDU REACTORS M. Stnciulescu, A. Dinu, M. Mihalache 7. THE WHY WHAT AND HOW IN NUCLEAR KNOWLEDGE MANAGEMENT Cristian Voiculescu, Eleonora Andreea Dragan 8. INVESTIGATION OF THE OXIDES FORMED ON 304L ODS STEEL AND 304L SS IN SUPERCRITICAL WATER ENVIRONMENT Maria Mihalache, Manuela Fulger, Constantin Paunoiu, Mihail Mihalache 9. THE DECOMMISSION AND UPGRADING OF TRITIUM LABORATORY FROM NATIONAL INSTITUTE FOR PHYSICS AND NUCLEAR ENGINEERING, MAGURELE C. Postolache, C. S. Tuta, Gh. Bubueanu, V. Fugaru, Diana Chiper 10. BEHAVIOUR OF FLUOROPOLYMERS IN PRESENCE OF TRITIATED WATER C. Postolache, Gh. Bubueanu, C. S. Tuta, V. Fugaru
11. RESEARCH PROGRAM OF ICIT ON TRITIUM FIELD AS SUPPORT FOR FUSION PROGRAM Marius Valentin Zamfirache, Anisia Mihaela Bornea, Ioan Stefanescu, Carmen Varlam, Nicolae Bidica 12. COLD NITROGEN RECOVERED USE TO INCREASE PERFORMANCE IN THE CRYOGENIC PILOT PLANT PURIFICATION MODULE Gheorghe Popescu, Sorin Gherghinescu, Ionut Spiridon, Marian Vacaru 13. 3D SIMULATION OF A DEUTERIUM STORAGE SYSTEM Eusebiu Ionete, Bogdan Monea, Roxana Ionete, Christoph Plusczyk 14. PROPAGANDISTIC VERSUS PROBABILISTIC RISK LEVEL OF ACCIDENTS IN NUCLEAR SAFETY ANALYSES Gheorghe Florescu, Ioan-Bogdan Florescu
SECTION 5: Hydrogen and Fuel Cells

1. HEAT TRANSFER MODELLING OF STEAM METHANE REFORMING Elena Carcadea, Mihai Varlam, Ioan Stefanescu, Mihai Culcer, Mariana Iliescu, Enache Adrian, Vasile Tanislav, Catalin Capris 2. COMPOSITE NAFION/TiO2 MEMBRANES FOR PROTON EXCHANGE MEMBRANE FUEL CELLS D. Ebrasu, G. Dorcioman, E. Axente, I.N. Mihailescu, L. Patularu, D. Schitea, M. Varlam, I. Stefanescu, L.M. Constantinescu 3. MATHEMATICAL MODELING OF CATALYTIC HYDROGENATION PROCESS OF GLYCEROL TO PROPYLENE GLYCOL Adriana Marinoiu, Claudia Cobzaru, Elena Carcadea, Vasile Tanislav, Catalin Capris 4. EXPERIMENTS REGARDING THE EFFECTS OF ISOTOPIC SEPARATION IN PEM ELECTROLYSERS Mariana Iliescu, Mihai Varlam, Roxana Elena Ionete, Mihai Culcer, Mihai Balan 5. PARAMETRICAL STUDY OF STEAM METHANE REFORMING IN A MEMBRANE REACTOR Elena Carcadea, Mihai Varlam, Ioan Stefanescu, Adriana Marinoiu, Vasile Tanislav, Catalin Capris 6. NEW CONCEPTUAL DESIGN FOR PEM FUEL CELL Anghel Vasile 7. OVERVIEW ON RENEWABLE ENERGY SOURCES HYDROGEN PRODUCTION USING THE ELECTROLYSIS PROCESS M. Balan, M. Culcer, I. Iordache, L. Patularu, A. Ciocan 8. ELECTROCHEMICAL CHARACTERIZATION FOR DIFFERENT TYPES OF GRAPHENE SUBSTRATES Ana-Maria Ducu, Stefan-Marian Iordache, Catalin Ceaus, Laurentiu Popovici, Adriana Balan, Ioan Stamatin
SECTION 6: Environmental and Life Quality

1. LIFE AND ENVIRONMENTAL PROTECTION BY DEVELOPING NEW INNOVATIVE SOLUTIONS FOR THE SAFETY OF BUILDINGS, SYSTEMS AND EQUIPMENT TO VIOLENT SEISMIC MOVEMENTS (EARTHQUAKES) Viorel Serban, Adrian Panait, Madalina Angela Zamfir, George Alexandru Ciocan, Marian Androne, Laura Elena Serban, Liviu Dan Postolache, Viorela Maria Postolache 2. ENVIRONMENTAL PROTECTION BY DEVELOPING EFFICIENT SOLUTIONS FOR THE COLLECTION, STORAGE AND REUSE OF RENEWABLE ENERGY Viorel Serban, Adrian Panait, Madalina Angela Zamfir, George Alexandru Ciocan, Marian Androne, Laura Elena Serban, Liviu Dan Postolache, Viorela Maria Postolache 3. EVALUATING MACROMINERALS CONTENT OF BONE MEAL POWDER Claudia Sandru, Felicia Bucura, Marius Constantinescu 4. THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE INDUSTRIAL AREA OF RM. VALCEA Mihaela Iordache, Ioan Viorel Branzoi, Ioan Iordache, Nicoleta Georgeta Dobre, Georgeta Totea 5. EDUCATION FOR SUSTAINABLE DEVELOPMENT Oana Ramona Grigoriu, Ionela Halcu, Giorgian Neculoiu, Virginia Cristiana Sndulescu, Alexandru Viorel Marinescu, Mariana Marinescu 6. LOG-NORMAL DISTRIBUTION OF THE SUSPENDED PARTICULATE MATTER (PM10) APPLICATION IN CRAIOVA, ROMANIA (2012) Liana Simona Sbirna, Teclu Codresi, Anisoara Oubraham, Sebastian Sbirna 7. MATHEMATICAL MODELS USED IN DESCRIBING AIR POLLUTANTS DISPERSION APPLICATION IN CRAIOVA, ROMANIA (2012) Teclu Codresi, Sebastian Sbirna, Liana Simona Sbirna, Anisoara Oubraham 8. VARIATION OF THE OLT RIVER QUALITY INTO THE INDUSTRIAL COMPLEX AREA OF RAMNICU VALCEA Mihaela Iordache, Branzoi Ioan Viorel, Ioan Iordache, Luisa Roxana Popescu, Maria Taralunga 9. DETAILED CHARACTERIZATION AND PROFILES OF AMBIENT ATMOSPHERE MONITORING USING AUTOMATIC TECHNIQUES FROM IN SITU COLLECTED SAMPLES Diana Florescu, Roxana Ionete, Felicia Bucura, Marius Constantinescu, Gili Saros 10. METHODS USED TO ESTIMATE THE GREENHOUSE GAS EMISSION POTENTIAL FROM SOLID WASTE DISPOSAL E. David, N. Aldea, S. Preda, A. Armeanu, C. Sandru, F. Bucura, M. Constantinescu, D. Mocanu 11. STUDIES ON THE IMPORTANT POLLUANTS OF WASTEWATER FROM TEXTILE INDUSTRY Claudia Sandru, Elena David, Felicia Bucura, Marius Constantinescu 12. PREPARATION METHODS FOR TRITIUM LIQUID SCINTILLATION ANALYSIS FROM ENVIRONMENTAL SAMPLES Carmen Varlam, Irina Vagner, Daniela Marinescu, Ionut Faurescu, Denisa Faurescu, Diana Bogdan 13. EVALUATION OF THE DEUTERIUM MODULATION POTENTIAL OF LEAD STATUS ON Zea mays ORGANOGENESIS AND GROWTH Gallia Butnaru, Ioan Sarac, Gheorghe Titescu, Horia Butnariu
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14. AEROSOLS ON THE BLACK SEA SHORE: A STUDY USING SUNPHOTOMETER MEASUREMENTS Sabina Stefan, Gabriela Raducan 15. PARAMETERIZATION OF THE BACKGROUND CONCENTRATION TO IMPROVE THE OSPM PERFORMANCE Gabriela Raducan 16. SYNTHESIS AND CHARACTERIZATION OF HIGHLY ORDERED SBA-15 FOR RETENTION OF POLYPHENOLS FROM RED WINE Violeta Niculescu, Andrea Iordache, Roxana Ionete, Nadia Paun, Viorica Parvulescu 17. ENVIRONMENTAL IMPACT OF PRIORITY HAZARDOUS SUBSTANCES ACCUMULATING IN SOIL, WATER AND SEDIMENT IN THE INDUSTRIAL AREA OF RAMNICU VALCEA Mihaela Iordache, Ioan Viorel Branzoi, Ioan Iordache, Georgeta Totea, Nicoleta Georgeta Dobre 18. CONSIDERATIONS CONCERNING THE INFLUENCE OF B20 BIODIESEL BLEND ON URBAN BUSES OPERATION AND MAINTENANCE Adrian Roca, Daniela Roca, Gabriel Vldu 19. ANALYSIS OF IDEALIZED TROPICAL CYCLONE SIMULATIONS USING THE WEATHER RESEARCH AND FORECASTING MODEL Gabriela Raducan, Roxana Elena Ionete, Ioan Stefanescu 20. BIODIESEL PRODUCTION USING MICROALGAE T. A. Costache, L. Popovici, I. Stamatin
SECTION 7: Laboratory Analysis Methods

1. ACTIVE THERMOGRAPHY NON-DESTRUCTIVE & NON-CONTACT MATERIAL TESTING Marius Popovici 2. COMPOUND-SPECIFIC CARBON ISOTOPE ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS USING GAS CHROMATOGRAPHY COMBUSTION ISOTOPE RATIO MASS SPECTROMETRY GC-C-IRMS Diana Costinel, Geana Irina, Ionete Roxana, Dinca Oana 3. AN OVERVIEW OF ANALYTICAL TECHNIQUES FOR PETROLEUM HYDROCARBONS CHEMICAL FINGERPRINTING Irina Geana, Raluca Popescu, Diana Costinel, Roxana Elena Ionete 4. ASSESSMENT OF THE ENVIRONMENTAL FATE OF -HEXACHLOROCYCLOHEXANE USING COMPOUND-SPECIFIC STABLE ISOTOPE FRACTIONATION ANALYSIS (CSIA) AND ENANTIOMER-SPECIFIC STABLE CARBON ISOTOPE ANALYSIS (ESIA) Silviu-Laurentiu Badea
SECTION 8: Agriculture and food safety

1. PHYSICAL AND CHEMICAL CHARACTERIZATION OF FLAVORED AND DEMY FLAVORED WINES FROM RECAS VINEYARD Ecaterina Lengyel, Letitia Oprean, Kettney Otto, Ramona Iancu, Bociu Diana, Ovidiu Tita 2. PHYSICOCHEMICAL AND MICROBIOLOGICAL CHARACTERISTICS OF BRANCOVEANU, GURA MINEI AND OCNITA LAKES, AS REPRE-SENTATIVE FOR THE LACUSTRINE COMPLEX FROM OCNA SIBIULUI Diana Bociu, Ecaterina Lengyel, Roxana Ionete 3. WINE QUALITY ASSURANCE USING MASS SPECTROMETRY TECHNIQUES Oana Romina Dinca, Roxana Elena Ionete, Diana Costinel
SECTION 9: Addendum
1. HYDROGEN - PAST, PRESENT AND FUTURE Ioan Stamatin 2. USE GIS TEHNIQUE TO ENVIRONMENTAL MONITORING IN AN INDUSTRIAL ZONE AND A GREEN AREA Gili Saros, Diana Florescu, Irina Geana, Raluca Popescu, Andreea Maria Iordache, Roxana Ionete 3. INSTALATIE PILOT PENTRU PRELUCRAREA PRIN DISTILARE IN VID A ULEIURILOR MINERALE UZATE. TESTE PRELIMINARE PILOT PLANT FOR PROCESSING USED MINERAL OILS BY VACUUM DISTILLATION Floarea Pop, Cornelia Croitoru, Emil Zaharia, Dorin Bombo], Elisabeta Pop 4. CERNAVODA NPP SOURCE TERM AND DOSE REDUCTION Catalina Chitu, Ioan Plaesu, Ion Popescu
Plenary Lectures
P Pl en na ar ec ur es le ry yL Le ct tu re s
ECOSYSTEM OF INNOVATIONS IN NANOTECHNOLOGIES FOR SAFETY, SECURITY AND SUSTAINABILITY Prof. Dr. Ashok Vaseashta
Institute for Advanced Sciences Convergence and Intl Clean Water Institute NUARI, 13873 Park Center Rd. Ste.: 500, Herndon, VA 20171 USA ACVC/VTT, U.S. Department of State, Washington DC 20520 USA ABSTRACT
The geopolitical landscape of the 21st century has become rather complex, dynamic, and unpredictable than that faced in the previous century. Notwithstanding unparalleled level of technological advancements, the evolving asymmetric threat from non-aligned terrorist groups continues to grow and evolve. The rapid advances in both science and technology, coupled with universal access to the internet have inspired both state and non-state sponsored actors to a new levels of creativity in the development of novel and non-traditional agents. Implementation of effective countermeasures demands an understanding of transformational emerging sciences, concepts and theories, and their potential applications. Numerous technological advances arise from the potential of nanoscale materials to exhibit unique properties that are attributable to their small size. Furthermore, advances in material synthesis, device fabrication and characterization have provided the means to study, understand, control, or even manipulate the transitional characteristics between isolated atoms and molecules, and bulk materials. Consequently, various designer materials capable of producing devices and systems with remarkable, tunable, and desired properties have recently been fabricated. Such advances coupled with information technology, cognitive sciences, biotechnology, artificial intelligence, and genetics offer an ecosystem of innovations and potential pathways to counter threat vectors in ways never imagined possible earlier, such as deployment of systems with enhanced capabilities, information gathering, and thwarting threat at point-of-origin (PO2). This presentation provides many examples of such innovations using nanomaterials, such as in sensors/detectors, employing materials, phenomena, and effects including multilayer semiconductor structures, specially formulated interfaces, and exploiting different regions of electromagnetic spectrum provide various functionalities. Mechanisms such as refractive and nonlinear effects, absorption of electromagnetic radiation, fluorescence, avalanche phenomena for the detection of small fluxes of optical radiation, remote detection of explosives by neutron radiation, etc., provide additional sensing capabilities, in conjunction with algorithms for complex processing of information, providing end-to-end strategic assessments and modeling of mixed and complex hazardous environments to delineated signal from background interactions. Recent radiation sensors based on polymeric materials have gained significant technological attention. Furthermore, it is widely known that drinking water distribution systems are vulnerable to intentional and/or inadvertent contamination. Such contamination can be accomplished with classic and non-traditional chemical agents, toxic industrial chemicals (TICs), and/or toxic industrial materials (TIMs). Novel nanomaterials based sensors produce an e-tongue configuration to identify several contaminants in aqueous environments. The advancement of molecular biology and bio-mimetic using siderophores has several applications in environmental microbiology due to its ability to rapidly detect waterborne microbial pathogens. The overall scope encompasses abilities to sense, detect chemical-biological-radiological, nuclear, high yield explosive, and water borne contaminants all from safety and security standpoint. Thus, in order to provide accurate intelligence, surveillance, preparedness and interdiction of such combative postures, advances in S&T offers prudent preparedness. Keywords: sensors, detectors, safety, security, nanomaterials
The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
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P Pl en na ar ec ur es le ry yL Le ct tu re s
DETERMINATION OF TRITIUM BY ELECTROLYTIC ENRICHMENT IN ACCREDITED LABORATORY Jasmina Koar Logar, Denis Glavi Cindro
Joef Stefan Institute, Jamova cesta 39, SI-1000 Ljubljana, Slovenia + 386 1 477 3293, fax + 386 1 477 3151, e-mail: jasmina.logar@ijs.si; denis.cindro@ijs.si
ABSTRACT The tritium content in the environment is a consequence of natural and anthropogenic processes. It is usually included in the national radiological environmental monitorings as well as in the special monitorings in the surroundings of nuclear power plants and other nuclear objects. Tritium is also the ideal tracer for hydrological studies and its analyses are commonly performed in several commercial and research laboratories. In EU member states, the accreditation according to ISO/IEC 17025 standard for laboratories which are involved in national monitoring programs is common practice.Similar approach is adopted also in many others countries to assure the traceability, correctness and reliability of the results of tests performed in the laboratories. The analyses of tritium for hydrological purposes become a state of the art because of diminishment of so called bomb peak. Laboratories use requirements of ISO/IEC 17025 standard to implement a quality system aimed at improving their ability to consistently produce valid results. Some countries have additional directiveswhich prescribe also the method for determination of tritium in national monitorings. In Slovenia, the electrolytic enrichment and accreditation are obligatory for tritium measurements in the frames of the national monitoringprogrammes. The electrolytic enrichment method for tritium analysis consists of primary distillation, electrolytic enrichment, secondary distillation, LSC counting and the analysis of measurement results. Conductivity and pH are tested during the whole process as well as all equipment involved. The method of electrolytic enrichment as well as quality system, the main control charts and their effect to the final results will be presented and described.
NITRIDE NUCLEAR FUELS Damian Axente

National Institute for Research and Development of Isotopic and Molecular Technologies 400293 Cluj-Napoca, 65-103 Donath Str. P.O.Box 700, Romania Tel.: +40264584037; Fax.: +40264420042, E-Mail: Damian.Axente@itim-cj.ro
ABSTRACT
The properties of U, PuN and U2N3, in comparison with of (U, Pu)C, (U, Pu)O2 and UPuZr alloy, are presented. The variation of thermal conductivity of different actinide nitrides and oxides with temperature is also shown. UN has the best thermal conductivity for the temperature interval of 500-2500C, compared with the Np, Pu, Am nitrides and (U, Pu)O2. Some others properties make nitride fuels attractive for fast reactors: - high solubility rate in nitric acid, which makes them compatible with PUREX process, the most common and cheap process for fuel recycling and reprocessing. - a high burn-up to 20%, proven in the fast reactor BOR-60 - low fission gas release to the fuel pin plenum, compared to oxide fuels. Some drawbacks of the nitride fuel are:
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P Pl en na ar ec ur es le ry yL Le ct tu re s - the (n, p) reaction of 14N, giving 14C radioactive, forces to use the stable isotope 15N, which has a very low cross section for neutrons. - due to the very high affinity of nitrides for oxygen, the whole production process must be done in a controlled atmosphere. - as a ceramic fuel, it has a small creep rate induced by irradiation, that has to be taken into account to avoid the pellet-clad mechanical interaction. The most studied synthesis method of a nitride nuclear fuel, starting from metallic uranium, has the following steps: hydriding the metallic uranium to get UH3; nitriding the produced hydride to U2N3 and dinitridation of U2N3 to UN. Starting from Uranium or Plutonium dioxide, the conversion into nitride consists in: carbothermic nitridation of UO2 or PuO2 in a nitrogen-hydrogen atmosphere and decarburization in the same gaseous atmosphere. The sol-gel method for preparation of the nitride type nuclear fuels is based on the internal gelation of feed solutions containing urea, hexamethylentetramine (HMTA) nitric acid and a metaloxonitrate. Droplets of the feed solution are heated up in hot silicon oil, which accelerates the protonation and decomposition of HMTA. The produced ammonia initializes the gelation process and solution droplets become solid microspheres. During the sintering step a carbothermic nitridation takes place and sintered nitride microspheres of high quality are obtained. By heating an UF4 sample at 800oC in ammonia atmosphere the U2N3 was obtained; at 1100oC it passes to UN of following composition: 93.17% U; 5.14% N and 1.69% O. Some impurities have been reduced by heating for longer time period under NH3 atmosphere.
Acknowledgment: This work was supported by ASGARD FP7-Euratom project, entitled: Advanced Fuels for Generation IV Reactors: Reprocessing and Dissolution, in which INCDTIM Cluj-Napoca is partner.
RESERVED TITLE Mihai Varlam

National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250.732.744; fax: 0250.732.746
RESERVED TITLE Liviu Stefan

National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250.732.744; fax: 0250.732.746
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Stable Isotopes Physics, Technologies and Applications
S ab eI es Ph hy ,T Te ec hn no gi es an nd d A Ap at ns St ta bl le Is so ot to op pe sP ys si ic cs s, ch ol lo og ie s a pp pl li ic ca ti io on s
EXPERIMENTAL EVIDENCES OF THE INFLUENCE OF NITROGEN GAS ON THE TRIMER IONS IN LOW RESOLUTION MASS SPECTROMETRY OF HYDROGEN ISOTOPES N. Bidic, G. Bulubaa
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250.732.744;
fax: 0250.732.746; E-mail: Nicolae.Bidica@icsi.ro
ABSTRACT
This paper presents experimental results regarding the behaviour of triatomic (trimer) ions formed in the electron impact ion source of a mass spectrometer in the presence of high concentrations of nitrogen gas. These results were obtained during an experimental work performed in order to find solutions to correct the total ion currents (measured at masses of interest) that are affected by isobaric interferences in low resolution mass spectrometry of hydrogen isotopes. A commercial quadrupole mass spectrometer of unit resolution, equipped with an electron impact ion source, was usedto analysehigh purity H2 and D2 and several H2/N2 and D2/N2 mixtures (of different concentrations). The results show a high influence of nitrogen gas on trimer ions, and this influence could be used to develop new procedures for hydrogen isotopes measurement by low resolution mass spectrometry. Keywords: hydrogen isotopes, mass spectrometry, triatomic ions (trimers).
THE ACCURACY OF FOURIER TRANSFORM INFRARED SPECTROSCOPY METHOD USED TO QUANTIFY THE DEUTERIUM CONCENTRATION IN HEAVY WATER STANDARDS Gabriela Raducan, Iuliana Piciorea, Ioan Stefanescu
National Institute for Research and Development for Cryogenics and Isotopic Technologies ICIT- Rm. Valcea, Romania, e-mail: gabi_raducan@yahoo.com; iulianap@icsi.ro
ABSTRACT
The aim of this study is to estimate the uncertainty of the FT-IR spectroscopy method in heavy water concentration measurement. A total of 8 samples were prepared over the concentration from 99,165 to 99,924 % D2O, using D2O primary standard of 99.961% D2O obtained from AECL and appropriate amount of ultrapure water. The deuterium concentration of heavy water samples was obtained using the gravimetric method. The FT-IR spectroscopy method is used to record the heavy water InfraRed spectrogram. A FT-IR spectrometer Nicolet 6700 was used to build a calibration curve, using these samples as standards. This device is not able to bring the sample at a preset temperature, but the temperature can be kept at a certain value with the air conditioning. The uncertainty of the method was estimated. This value is very low compared with the uncertainty estimated with the vibrational densimetry method, so this method can be used in the range of deuterium concentrations higher than 99% D2O mass, where it is necessary a very good measurement accuracy. Keywords: D2O; heavy water; deuterium concentration, Ft-IR spectroscopy, uncertainty. The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 19
Cryogenics Technologies and Equipments
C ge en ni Te ec hn no gi es an nd d E qu ui en nt Cr ry yo og ic cs sT ch ol lo og ie sa Eq ip pm me ts s
THERMAL AND MAGNETIC DESIGN OF A HTS HIGH MAGNETIC FIELD GENERATOR USING SUPERCONDUCTING HELMHOLTZ COILS Ion Dobrin1, Alexandru Morega2, Adrian Nedelcu1, Mihaela Morega2, Dan Daniel1
Institutul National de Cercetare Dezvolatare pentru Ingineria Electrica ICPE-CA, Splaiul Unirii nr. 313, sector 3, Bucuresti, tel. 021.346.7231, Fax. 021.346.8299, e-mail: ion.dobrin@icpe-ca.ro 2 Universitatea Politehnica din Bucuresti Facultatea de Inginerie Electrica, Splaiul Independentei nr. 313, sector 6, Bucuresti, e-mail: amm@iem.pub.ro
1
ABSTRACT
This paper is concerned with the analysis of thermal and magnetic design of a high uniformity magnetic field generator using Helmholtz superconducting coils, usable in particle accelerators or nuclear physics experiments. The aim is the construction of a 3 T dipole magnet system, cooled by a closed-cycle cryocooler Gifford-McMahon type with two cooling stages: 50 K for first stage and 4.2 K for the second stage. The Helmholtz coils are made of High Temperature Superconductor (HTS) tape of YBCO type. We present a mathematical model and finite element (FEM) experiments performed on the dipolar Helmholtz Magnet for high magnetic field uniformity. Our study is based a the three dimentional, CAD model of the system protopype. The numerical simulation results unveil the magnetic field spectrum and the heat paths within the agregate structure of the magnet system. Keywords: Helmholtz coils, high uniformity magnetic field, high temperature superconductor, cryogenics, thermal analysis, numerical simulation, finite element.
1. INTRODUCTION One of the most important factors for successful development of any superconducting magnet system (SMS) is the cooling technology. For relatively many years the only possibility to cool down a superconducting magnet system was the use of cryogens (liquid helium, liquid hydrogen or liquid nitrogen). In the last decades a new cooling technology (cryogen-free) has made increasing progress and became the preferred one instead of cryogens, because of its simplicity, compactness, easy handling and higher efficiency. So, many superconducting magnet systems have been designed to use just cryocoolers for reaching low and very low temperatures [1]-[5]. The cryocooler acts as a heat pump, taking out the system heat by direct conduction and lowering the system temperature to de desired values. In a conduction cooled superconducting magnet system, a two-stage G-M cryocooler is employed as a heat sink to cool the magnet down to the designed temperature. Since the cold head of a cryocooler has positional restrictions, it needs to be located in a low magnetic field area to avoid degradation of its refrigeration capacity. Thus, a conductive link between the magnet and the cryocooler is important in developing the superconducting magnet system. The paper presents a HTS magnet in Helmholtz configuration, continuously refrigerated by a two-stage G-M cryocooler, in order to produce a 3T magnetic field, aimed for use in particle accelerators or nuclear physics experiments. The HTS superconducting magnet and the cooling system are designed based on the associated analysis. The superconducting coils, current leads and the cryogenic cooling system are integrated and the thermal influx towards the HTS coil system is evaluated by numerical methods. By adequate methods, 2D numerical simulations are employed for the generated magnetic field optimization with respect to the field uniformity.
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This numerical analyze aims to obtain the optimal thermal functioning conditions for the designed HTS magnet system, cooled by direct conduction in order to generate a high intensity magnetic field (3T) with high uniformity (~10-3). 2. THE HTS MAGNET SYSTEM The schematic of the superconducting magnet system directly cooled by a cryocooler is shown in fig. 1 c. The main components of the superconducting magnet system are: the superconducting Helmholtz coils, the cooling system and the cryostat. The HTS pancake type coils are wounded around the magnet holder, which is thermally connected to the second stage cold head of a cryocooler through a conductive link. The room temperature bore, made of nonmagnetic stainless steel with a 30 mm diameter is located in the middle of the HTS coils winding.
a. The superconducting magnet system.
b. CAD design.
c. Schematic of the superconducting magnet system. Figure 1. The HTS magnet with direct cooling system. The current leads used in this system are combination of normal conductor (copper) and HTS conductor, thermally connected to the first stage of the cryocooler. A high purity aluminum radiation shield and a multilayered super insulation, positioned between the outer wall of the cryostat and the shield (at room temperature), insulate the cold part. The thermal shield is attached to the first stage flange of the cryocooler. The main parameters of the SMS cooled by are summarized in Table 1.
24 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
Table 1. The main parameters of the HTS superconductor magnet system Parameter Value Central field 3 HTS wire YBCO Main field coils: 2 - inner diameter 30 110 - outer diameter - length 35 Coil turns 3602 Operating current 150 Operating temperature Cryostat dimensions: 4.5 - main diameter - height 260 - bore diameter 650 30
Units T mm mm mm A K mm mm mm
A. The Helmholtz Superconducting Magnet The HTS coils were fabricated by the wet winding method using Stycast type epoxy for coil impregnation. The HTS composite superconducting wire, YBCO type, 4.5 mm wide and 0.22 mm thick, was wounded on the copper holder, which has a 1 mm slot along the axis in order to reduce eddy currents losses during the magnet charging process. A coil is of double pancake type and the two HTS coils are in a Helmholtz arrangement, in order to obtain a 3T high uniformity magnetic field of fourth order compensated. The total length of superconducting wire was 75m/coil and the overall mass of the magnet around 4.25 kg. The two current leads comprise a copper element, to conduct the current from room temperature to an intermediate temperature (50 K) and a HTS element, conducting the current down to 4.5 K. The copper element was optimized to minimize the cryogenic load. The minimum heat load per unit current of copper element is 0.040 W/A when the optimum lead parameter of copper is 2500 A/mm. The CryoSaverTM current lead from HTS-110 was used as an HTS current lead for this system between 50K and 4K. The operating current is 250 A, at 64 K, and the conducting heat is about 175 mW [6]. B. The Cryogenic System The HTS magnet holder is thermally coupled onto the second stage cold head of the cryocooler through a copper plate of 12 mm thick and thermal conductive flexible tinned copper braids. Cryogenic grease is applied between copper support of the coils and cold head of cryocooler as a thermal contact medium, ensuring maximum thermal conductance. A copper shield was suspended from the plate of the 1st stage cold head and thermally connected to it. The cryogenic loads were estimated using relevant analysis and summarized in Table 2. It is worth mentioning that the total heat load for each stage matched the refrigeration capacity of the two stages Gifford-Mc-Mahon cryocooler (Sumitomo RDK-415D) [7], with 35 W cooling capacity at 50 K for the 1st stage and 1.5 W cooling power at 4.5 K for the second stage. Table 2. Estimated heat load 1th stage 18.50 1.80 13.50 33.80
Thermal influx [W] Current leads, by conduction Measurement wires Radiation Total thermal load [W]
2nd stage 0.35 0.12 1.02 1.49
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3. MATHEMATICAL MODELING AND NUMERICAL IMPLEMENTATION Two major problems are of concern to the proper functioning of the SMS the heat transfer problem and the magnetic field problem and both are solved for in our study by mathematical modeling and numerical simulation. A. The Heat Transfer Problem The SMS coils operate below 4 K thus the heat inflow from the ambient has to be diminished such that the temperature stays within safe limits. The thermal design is then to combine conduction heat transfer parts and radiation shielding to limit the heat leakage. As the HTS coils operate in the superconductor regime, the Joule effect is negligibly small, therefore the sole heat source is the boundary (the case). The first objective is then to size a composite structure made of thermal shields and vacuumed cavities to limit the heat influx, to be conveyed to the external cryostat this is the second objective. The steady state conduction heat transfer in the SMS cooling system is described by the energy equation k 2 (1) T=0, c p where [kg/m3] is the mass density, cp [J/(kgK)] is the specific heat at constant pressure, k [W/(m K)] is the thermal conductivity, and T [K] is the temperature. In this study, the thermal properties are assumed constant, temperature independent. As radiation heat transfer is of concern, complex structures such as that of the SMS, analytic solutions (if any) are not readily available, therefore numerical heat transfer design relying on 3D computational domains (e.g., produced by CAD) has to be used. Table 3 lists the relevant heat transfer properties used throughout the numerical simulations. Table 3. Heat transfer properties Thermal influx Thermal conductivity, k [W/(mK)] Emissivity, Stainless steel @ 80...300 K 0.12 44.5 Copper shields @ 80300 K 0.06 400 Copper shields @ 480 K 0.02 400 The BCs that close the problem are as follows (Fig. 2): The shell (case)
T = Tamb ,
(2)
Symmetry planes (adiabatic)

n kT = 0 ,
(3)
Shields surfaces (surface to surface radiation)
(1 )G = J
T 4 .
(4)
Here, is the emissivity (Tab. 3) = 5.67108 W/(m2T4) is Stefan-Boltzmann constant, Tamb = 300 K is the ambient temperature, G [W/m2] is the incoming radiation heat flux (irradiation), and J0 [W/m2] is the surface radiosity.
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Twarm = 50 K Tamb = 300 K
Symmetry Symmetry
Tcold = 4 K
Figure 2. The boundary conditions in the heat transfer problem. The mathematical model (1)-(4) is solved by the Galerkin finite element (FEM) technique, as implemented by [8]. The problem is reduced to quarter by symmetry reasons. Fig. 3 shows the FEM mesh network used for the numerical simulations.
Figure 3. The computational domain FEM mesh made of approx. 230,000 Lagrange linear elements. B. The Magnetic Field Problem Considering the axial symmetry of the Helmholtz coils, it is possible to simplify the magnetic field problem to a 2D (axial symmetric) model. Fig. 4.a shows the computational domain. Each side of the Helmholtz assembly is made of two planar coils made of tape conductor. The small gap (0.5 mm) accounts for the resin filling used to mechanically strengthen the coils. The magnetic field (azimuth currents, total, gauged, magnetic vector potential) is described by the partial differential equation (PDE)
1 1 e 0 r A = J .
(5)
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a. The computational domain. b. The FEM mesh. Figure 4. The 2D model of the magnetic field problem.
e [A/m2] is where A [Tm] is the magnetic vector potential (only the angular component, A), and J the external electrical current (source, in the windings); 0 is magnetic permeability of vacuum. The FEM mesh (Fig. 4.b) consists of 47,444 triangular elements, with a fine meshing area for the central region of the coils (r < ri). The size of the finest mesh triangles is 0.5 mm, while for the surrounding space it is at most 1 mm. The radius of the circular containing space (computational domain) is 120 mm. Tangential flux and symmetry boundary conditions close the model.
4. NUMERICAL SIMULATION RESULTS AND DISCUSSION A. Heat Transfer by Numerical Simulation The SMS coils operate below 4 K thus the heat inflow from the ambient has to be diminished such that the temperature stays within safe limits. The thermal design is then to combine conduction heat transfer parts and radiation shielding to limit the heat leakage.
Figure 5. The temperature field within the magnet. Fig. 5 shows the temperature field through surface color map (color proportional to the local temperature). The vacuumed cavities are void (discarded from the computation) hence the shields and case are observable. Three regions are noticeable: the steel case (high temperature, 300 K), the first and second stage casing shields (low temperature, below 50 K), and the working duct that crosses the entire
structure. A third casing (shielded), inner to the second, coils casing system, is provided to reduce the heat leakage from the duct to the Helmholtz coils. Table 4 lists the power thermal load to the two stages of the cryocooler. The results are in satisfactory agreement with the measured data, considering that the in the numerical model the Joule loses in the connecting wires are not accounted for. Table 4. Estimated heat load by numerical simulation Unit Heat (in)flux [W] Second stage cold chamber (through the cold head 2) 1.30 First stage cold chamber (through the cold head 1) 14.88 Total thermal load 16.18 B. Magnetic Field by Numerical Simulation Simulations were performed for two parameters: first the distance between coils in Oz axis direction, to find the optimum, and the excitation current, to determine the extent of the adequate field area (absolute error of the field below 0.01 T).
Optimal rezult: pid=4 d=0.014m =0.082205% =0.00246T r a 3.2 3.1 3 2.9 |B| [T] 2.8 2.7 2.6 2.5
0.011 0.012 0.013 0.014 0.015 0.016 0.017 0.018 0.019 optim
-20
-15
-10
-5
0 distance [mm]
10
15
20
Figure 6. The magnetic flux density along the axis of Helmholtz system for different distances. The initial distance between the two sides of the system is set to be equal to internal radius (ri). With respect to this position the coils are shifted from -4 to +4 mm apart from each other in Oz axis direction, with resolution of 1 mm. The results are shown in Fig. 6. The optimal distance is that which minimizes
r = Bmax Bavg Bavg
(6)
where Bmax and Bavg are evaluated on the 10 mm zone. We set the optimal distance and the supply current was varied from 50 to 281.57 A (for which B0 = 3 T). The size of the good field for each value of the supply current can be seen in Fig. 7.
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3.5 50 100 150 200 250 281.57
3.5
3 2.66 T 2.5 |B0| [T] 2.13 T 2 1.60 T
3.00 T
2.5
2 |B| [T]
B<0.01
1.5
1.5
1
1 1.07 T
0.5
0 -25
-20
-15
-10
-5 0 5 distance [mm]
10
15
20
25
0.5 0.53 T 50
100
150 Isupply [A]
200
250
300
Figure 7. Field on the axis of Helmholtz system for different currents. The magnetic field solution for the optimal case is given in Fig. 8 through the spectrum of the magnetic flux density.
Figure 8. The magnetic flux density surface color map. 5. CONCLUSIONS This work presents the functional parameters designed for a HTS magnet in Helmholtz configuration continuously refrigerated by a two-stage G-M cryocooler. The aim is to generate 3T magnetic field with high uniformity (~10-3) in an warm (300K) bore in order to be accessible outside. Numerical simulations were made for the heat flux evaluation towards the superconducting coils and the thermal protective shield. The results show good agreement with the heat load preliminary evaluations and they do not exceed the thermal cooling power of the G-M Cryocooler: 35W for 50K (first stage) and 1.5W at 4.2K (the second stage). These results show a proper design of the system. A 2D numerical simulation was done for the magnetic field generated by the HTS Helmholtz coil system in order to obtain the adequate conditions for the 3T magnetic flux density generation with 10-3 uniformity. The results were found for 30mm bore diameter, with 281.57 A current supply for the coils. The next step to accomplish this work is the realization and testing of the system. The final aim is to obtain a dry system to generate high magnetic fields with high uniformity to be used in
particle accelerators or nuclear physics experiments which requires such magnetic field parameters or higher. ACKNOWLEDGEMENTS This work was financially supported by the Romanian National Authority for Scientific Research through the Core Research Program. ICPE-CA acknowledges the funding under the Contract PN 0935102/2009. Numerical modeling and simulations were conducted in the Laboratory for Multiphysics Modeling at University POLITEHNICA of Bucharest.
REFERENCES 1. A. M. Morega, I. Dobrin, M. Morega, Thermal And Magnetic Design Of A Dipolar Superferric Magnet For High Uniformity Magnetic Field, 7th International Symposium on Advanced Topics in Electrical Engineering - ATEE 2011, May 12-14, Bucuresti, pp.589-592, IEEE no: CFP1114P-PRT, ISBN 978-1-4577-0507-6. 2. Y.Dai, Q.Wang, s.a., An 8T Superconducting Split Magnet System with Large Crossing Warm Bore, IEEE Trans. On Applied Superconductivity, Vol. 20, June 2010, pp. 608-611. 3. E. Demikhov, F.Kostrov, V.Lysenko, N.Piskunov and V.Troitskiy, 8T Cryogen free Magnet With Variable Temperature Insert Using a Heat Switch, IEEE Trans. On Applied Superconductivity, Vol. 20, June 2010, pp. 612-615. 4. F. Giebler, G. Thummes and K.J.Best, A 5T Persistent Current Niobium-Titanium Magnet with 4K Pulse Tube Cryocooler , Superconductor Science Technology, pp. 135-139, 2004. 5. Jing Shi, Yuen Tang, et al., Development of Conduction Cooled HTS SMES, IEEE Trans. On Applied Superconductivity, Vol. 17, 2007, pp. 3846-3850. 6. HTS-110 Co., http:// www.hts-110.com/current leads 7. Sumitomo Inc., http://www.shicryogenics.com 8. Comsol Multiphysics AB, v. 3.5a (2010), v. 4.2 (2011)
IMPORTANCE OF LOCAL LEAK RATE IN DETERMINATION OF GAS LEAK LOCALIZATION IN ENCLOSED INDUSTRIAL BUILDING Stefan-Ionut Spiridon, Sorin Gherghinescu, Gheorghe Popescu
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250/732744; fax:
0250/732746; E-mail: ispiridon@icsi.ro
ABSTRACT
Byproduct of electricity production by nuclear power plants, Tritium, is considered to be the main fuel source for fusion reactors. The tritiated water obtained in the fission reactors is transformed with the help of TRFs in pure tritium gas. This is further used as primary source in the fuel cycle of the fusion reactors. The technical assembly of the TRF (Tritium Removal Facility) is regarded as a complex system of specialized equipment, sensors, detectors, valves and piping arrangements. Working pressure and temperatures of the TRF system defines the types of sensors, the vacuum technology and especially the possible operational safety issues. Leaks in the systems represent one of the main safety issues in a TRF. Environmental and work safety regulations state that if leak from a system, in a closed or open The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 31
C ge en ni Te ec hn no gi es an nd d E qu ui en nt Cr ry yo og ic cs sT ch ol lo og ie sa Eq ip pm me ts s space, exceeds some threshold value it must be reported. Tritium has a special regulation because of its radioactive impact and its strategically importance. This article describes a calculation procedure that demonstrates that the leaks in the system could be localized and estimated. Using a least squares technique in a spreadsheet, parameters of a nonlinear equation can be determined for a localized leak in an enclosure, like a cold-box, e.g.. The calculations were based on a leak test using nitrogen and also industrial air. The pressure loss in the system was modelled by evaluating the leak through an orifice with specified open surface. This coefficient of opened surface was then used to calculate the loss of tritium in the system. The first step in the test was to fill the system. The pressure in the system was recorded as a function of time. This loss in pressure was described as proportional to the orifice coefficient. Keywords: leak rate, tritium, TRF, environment safety, work safety.
PRESSURE LOSS DETECTION IN PLANTS WITH CONTINUOUS MONITORING BY MEASURING THE FLOW PARAMETERS Sorin Gherghinescu, Stefan-Ionut Spiridon, Gheorghe Popescu
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250/732744; fax: 0250/732746; E-mail: sorin@.icsi.ro; sorin70g@yahoo.com
ABSTRACT
In this study, the thermo-dynamic characteristics of gases leak rate through a system have been studied. Different pressures versus time scenarios have been applied to a model system. Nitrogen and industrial air were used to perform the pressurized leak rate test. The thermal conductance influence was measured from both pressure-decay experiments and from constant pressure-flow experiments using gases at variable temperatures due the length of the gas supply piping. Results from the two type gas tests were compared and communicated in this paper. In the evaluation of real components, subassemblies, or systems, conductance and also the thermo-dynamical flow of the gas trough piping system of can be estimated from a simple pressure-decay measurement. Obtain values can be used to estimate the effect of thermal conductance on the leak rate, to minimize the construction complexity of the piping and also to improve the insulation factor of the refrigeration system. In cryogenic systems is important to determine the leakage of gas for the cooling power regulation and automation system. In the cryogenic distillation process gas purity and thermal regime are very important design features. This study establishes the parameters of the thermal control system and gas purity. By plotting discharge curves can be established the influence of change of parameters in the system and can locate the leakage occurred by measuring the corresponding flow. Discharge curves were plotted on an area covering the normal running of the plant. The experimental results obtained demonstrate the importance of continuous monitoring of flow in nuclear installations on the one hand due to ensuring the safety in operation and on the other hand to control the process parameters. Keywords: cryogenic systems, equilibrium parameters, pressure leakage.
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EXPERIMENTAL DETERMINATION OF FLOW PARAMETERS VARIATION TO LOCATE ANY MALFUNCTIONS FOR CONTINUOUS MONITORING INSTALLATIONS Sorin Gherghinescu, Ionu Spiridon, Gheorghe Popescu, Marian Vacaru
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250/732744; fax: 0250/732746; E-mail: sorin@.icsi.ro; sorin70g@yahoo.com
ABSTRACT
This study aimed to determine the gas flow characteristics by measuring the flow rate in a defined volume of a thermal system. Tests were performed at different pressures for discharged unit. As flow agents nitrogen and air were usedto determine the flow rate. Influence of thermal conductance was determined by measuring the temperature variation of the gasespolytropictransformations. Results from the two sets of tests were compared and reported in this paper. The values obtained can be used to estimate the thermal conductance effect on the leakage rate to minimize the complexity of pipeline construction also improving the insulation factor for the refrigeration system. In the cryogenic transformations is important to determine the flow of cooling power setting and system automation. In the cryogenic distillation process gas and thermal regime are important design features. This study establishes parameters for thermal control system and gas purity. The discharge curves plotting pressure over time have been set fornormal functioning system parameters. By measuring the corresponding flow, the leaks in the systems have been located. Unloading curves were plotted on an area covering normal operation of the facility. The experimental results obtained demonstrate the importance of continuous monitoring of flow in nuclear facilities, on the one hand due to ensuring safe operation and on the other hand, control of process parameters. Keywords: cryogenic systems, equilibrium parameters, flow characteristics.
HIGH QUALITY PURIFICATION OF DEUTERIUM FOR CRYOGENIC DISTILLATION SYSTEM FROM CTRF PROJECT Florina Porcariu, Mirela Drghia, Gheorghe Pasca
SC I.S.TECH SRL, Str.Timocului, Nr.T21, Ap.2 Cod 300107 Timisoara, Tel.: 0356 173 660 , Fax: 0356 173 660, E-mail florina.porcariu@istech-ro.com
ABSTRACT
The CTRF detritiation facility will be built for tritium removal and recovery from tritiated heavy water during the operation of CANDU reactors at Cernavoda NPP. This facility consists of several systems, including Cryogenic Distillation System. In order to maintain proper operation of the Tritium Removal Facility and more specifically long time operation of the cryogenic distillation columns, and to meet the safety requirements, high quality purification of the supplied gas to the cryogenic distillation columns is necessary. The purification is based on selective adsorption of gases at low temperature which is a method with wide range of use in gas separation processes. The correct sizing of deuterium purification unit is necessary for minimize the external heat input and also for reducing the thermal inertia of the system/installation. This work/paper shows the scheme of deuterium purification unit, the operating mode and the experimental results of cryoadsorbers sizing for deuterium purification . The purification of tritiated deuterium consists in adsorbtion on active charcoal at temperature of 40 K of any impurities such as water vapors, nitrogen and oxygen. Keywords: Purification, deuterium, cryogenic distillation, cryoadsorbers. The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 33
1. INTRODUCTION The CTRF detritiation facility consists of several systems, including Cryogenic Distillation System. The Cryogenic Distillation System consists of six main subsystems: Tritiated Deuterium Purification System; Coldbox and Cryogenic Distillation Columns; Gloves Box; Hard Shell Confinement; Helium Refrigeration System; Low and High tritium concentration Expansion Tanks. In order to maintain proper operation of the Tritium Removal Facility and more specifically long time operation of the cryogenic distillation columns, and to meet the safety requirements, high quality purification of the supplied gas to the cryogenic distillation columns is necessary. The tritiated deuterium purification consists in adsorbtion on active charcoal at temperature of 40 K of any impurities such as water vapors, nitrogen and oxygen, feeding in the first cryogenic distillation column. The method of deuterium purification on active charcoal at 40K is a high effective purification method , because the deuterium is cooling down to 40K and all the impurities become solid , and they are trapped on charcoal in solid form. Using adsorption method at temperatures below 77K for the purpose of deuterium purification, requires accurate knowledge of adsorption capacity and optimal operating conditions as well. For the nitrogen adsorption on charcoal at a temperature around 40K, information from [2] were used. Experimental results [1] confirm that the adsorption capacity increased with temperature decreasing, i.e from 300cm3/g corresponding to a temperature of 77K up to 1235 cm3/g for an adsorption temperature of ~ 45K. According to [1] the pressure variation from 1bar to 10 bar in the range of temperatures 40-50 K does not influence the adsorbtion process. By determining the adsorption capacity of nitrogen on active charcoal in the range of 4050K at an average speed adsorption of 33 mm/s [1] will provide conditions for an optimal design of adsorption system from cryogenic processes. 2. DEUTERIUM PURIFICATION PROCESS FROM THE CRYOGENIC DISTILLATION SYSTEM The Deuterium Purification System (Figure 1) processes the tritiated deuterium gas, supplied from the LPCE at a pressure above atmospheric pressure (130 180 kPa) and the dew point -750 Celsius which correspond to a water content of 0.0013 g/Nm3. Tritiated deuterium gas contains water vapors, small amounts of nitrogen, and traces of other frozen gases at liquid deuterium temperature. The content of nitrogen in the tritiated deuterium stream is 0.15 ppm. The other impurities, i.e., oxygen that are frozen at liquid deuterium temperatures are currently assumed to be at a concentration of less than 0.01 ppm. Deuterium purification system, consists of two branches similar as configuration, one is on service and the other is on regeneration process or standby. On each branch there is a heat exchanger which provides pre-cooling of gas before entering into the cryoadsorbers. In the precooler, the tritiated deuterium gas from LPCE system with the temperature of 295K, is cooled down to ~ 40K by heat exchangers in counter flow with low tritium deuterium gas of 25K extracted at the top of the first cryogenic distillation column.
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Figure 1. Deuterium Purification System From the precooler, the tritiated deuterium gas passes the cryoadsorber bed where the impurities such as water vapors, nitrogen and oxygen, will be adsorbed in solid form on active charcoal at temperature of 40 K. From the adsorber bed, the tritiated deuterium gas with the temperature of ~ 45K, pass further through the heat exchanger for advanced cooling down to ~ 25K. The advanced cooling of the gas is perform using an cooled helium stream from one high pressure helium line which feeds the CD column condensers. The regeneration of the cryoadsorbers and removing the impurities trapped in the feeding lines of the first CD column, shall be realized in two steps: a. The cryoadsorbers shall be heated up to 200K by a helium stream from the helium system for cryoadsorbers regeneration. The desorbed gases shall be sent for processing in to the TRS. b. Provisions in the configuration of the deuterium purification system are implemented to heat up the cryoadsorbers up to 400K and to remove the water with a deuterium stream which is circulated towards the LPCE. After the regeneration of the cryoadsorbers and removing the water trapped in the precooling and advanced cooling heat exchangers, a cooled helium streams from the high pressure helium line, in front of the CD condensers, shall be used to cool down the cryoadsorbers before enter in service.
3. SIZING THE CRYOADSORBERS FOR THE DEUTERIUM PURIFICATION SYSTEM The size of the cryoadsorbers is given by the amount of impurities contained in the deuterium stream coming from the LPCE . Considering a conservative value of 1.0 ppm for nitrogen content in deuterium stream at the inlet of the cryoadsorber, the water content of 0.0033 g/Nm3 (or equivalent to ~ 4 ppm) which corresponds to the dew point of - 70C , and the deuterium flow rate to be feed in the CD system of 3.2 kmol/h, the amount of water and nitrogen that have to be trapped in the cryoadsorbers during different periods of time between two regenerations is given in Table 1.
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Table 1. Amount of impurities to be trapped in cryoadsorbers Time in between two regenerations 1 month 3 month 6 month 12 month Amount of D2O to be trapped (kg) Amount of N2 to be trapped (Nm3) 0.2 0.051 0.6 0.155 1.2 0.31 2.4 0.62
Considering that the adsorbtion capacity of charcoal for water at 40 K is equivalent with 10% from the weight of charcoal bed and the adsorbtion capacity of charcoal for nitrogen is 300 cm3/g, [2],[3],[4],[5],[6] the amount of charcoal necessary for trapping the water and the nitrogen for various periods of time between two regenerations is given in Table 2. Table 2. Amount of charcoal needed to trap the water and the nitrogen Time in between two regenerations 1 month 3 month 6 month 12 month 2 6 12 24 Amount of charcoal needed to trap D2O (kg) 0,170 0,510 1,02 2,04 Amount of charcoal needed to trap N2 (kg) Based on the data from above and taking into consideration the safe margins in the input data, each cryoadsorbers shall be design to be filled with 15 kg active charcoal. Due to safe margins, the period in between two regenerations shall be established during commissioning in order to avoid unnecessary regenerations. 4. CONCLUSIONS The proposed method and the system configuration of the deuterium purification allow a high effective purification of the process gas, which provide efficient and safe operation of the CTRF facility. There is enough information in order to size the cryoadsorbers and good practice in industrial level. REFERENCES 1. Ion Cristescu, Marius Peculea Adsorbtia azotului pe carbine active la 40K dintr-un amestec de hydrogen Revista de Chimie Nr. 4/2002 2. S.D. BONDARENKO, I.A. ALEKSEEV - Petersburg Nuclear Physics Institute,188300, Gatchina, Leningrad dist., Russia Study of isotopic effect for hydrogen and deuterium adsorbtion on nanoporous carbon (NPC) AT 67-78 K - Hydrogen Materials Science and Chemistry of Carbon Nanomaterials, 493-497. 3. R. Yahik, U. Yanik, C. Heiden, University of Giessen, Germany Adsorbtion Izotherms and heats of adsorbtion of neoh and hydrogen on zeolyte and charcoal between 20K and 90 K Journal of low temperature Physics, vol 45, 1981 4. D. Basmadjian - Department of Applied Chemistry and Chemical Engineering, University of Toronto, Ontario. Adsorbtion equilibria of hydrogen, deuterium, and their mixtures. Canadian Journal of Chemistry Vol. 38 (1960 5. H. Takagi, H. Hatori, Y. Soneda - National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba West - Adsorptive hydrogen storage in carbon and porous materials, Materials Science and Engineering B108 (2004) 143-147.
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6. Nidia C. Gallego, Timothy D. Burchell- Carbon Materials Technology Group Metals and Ceramics Division Oak Ridge National Laboratory, Oak Ridge, TN 37831-6087, Carbon materials for hydrogen storage
DETERMINATION OF LOCAL LEAK RATE AND GAS LEAK LOCALIZATION IN INDUSTRIAL BUILDING Stefan-Ionut Spiridon, Sorin Gherghinescu, Gheorghe Popescu, Marian Vacaru
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm. Valcea, Romania, e-mail: ispiridon@icsi.ro
ABSTRACT
Tritium main fuel source for fusion reactors is a byproduct of electricity production in the nuclear power plants. Obtained in the fission reactors the tritiated heavy water is transformed by the help of TRFs in pure tritium gas. The TRF (Tritium Removal Facility) regarded as atechnical assembly is a complex system of specialized equipment, detectors,sensors, valves and piping arrangements. The working pressures and temperatures of the TRF system define the types of sensors, the vacuum technology used and especially the possible operational safety issues. Leaks in the systems represent one of the main safety issues in a TRF. From the Environmental and Work Safety Regulations point of view leaks from a system, in a closed or open space that exceeds some threshold value must be reported. Tritium has a special regulation because of its radioactive impact and its strategically importance. Thecalculation scheme presented in this article demonstrates that the leaks in the system could be estimatedandlocalized. Using a least squares method in a excel spreadsheet, parameters of a nonlinear equation can be determined for a localized leak in an enclosure, like a cold-box, e.g.. The calculations were based on a leak test using nitrogen and industrial air. The pressure loss in the system has been modelled by evaluating the leak through an orifice with specified open surface. This coefficient of opened surface was then used to evaluate and estimate a possible loss of tritium in the system, having the stationary gas characteristic of tritium. The pressure in the system was recorded as a function of time and the loss in pressure was described as proportional to the flow surface section characteristics. Keywords: leak rate,tritiated heavy water, environment safety, work safety
SOLUTII DE CONTROL UTILIZATE IN PROCESECRIOGENICE CU APLICATIE LA PILOTUL EXPERIMENTAL DE LA RM. VALCEA Sorin Brotac1,2, Alexandrina Dragoi1, Lucian Radu1,2, Sabin Chivescu1
1
CELIN SRL, Bucuresti; 2Asociatia pentru Automatizari si Instrumentatie din Romania
ABSTRACT
Sistemul de distilare criogenica reprezinta un proiect de un interes si o importanta deosebita, in principal datorita faptului ca reprezinta o instalatie experimentala din sfera domeniului nuclear. Sistemul de distilare criogenica are ca functie de baza separarea tritiului din deuteriul tritiat alimentat de sistemul de purificare. Distilarea criogenica este realizata de o cascada de patru coloane aflate intr-o incinta vidata, racirea necesara pentru distilarea deuteriului fiind asigurata de o unitate de refrigerare bazata pe un ciclu de racire The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 37
C ge en ni Te ec hn no gi es an nd d E qu ui en nt Cr ry yo og ic cs sT ch ol lo og ie sa Eq ip pm me ts s prin detenta heliului. Vehicularea fluxurilor de gaz intre cele 4 coloane de distilare se realizeaza prin intermediul unor pompe cu membrane care functioneaza la temperatura ambianta intr-o zona adiacenta. Tritiul este separat/concentrat in baza ultimei coloane de unde este extras in vederea stocarii. Adevarata provocare pentru controlul instalatiei consta in stabilirea punctelor de masura si a elementelor de executie, alegerea aparatelor (avand in vedere mediul deosebit criogenic, fluxurile tehnologice reduse si functionare continua 24/7) si stabilirea buclelor de control. Datorita mediului de lucru special temperaturi criogenice si vid inaintat se propun spre implementarii solutii adecvate constand in senzori de diode cu siliciu pentru temperatura, cabluri electrice speciale si incalzitori rezistivi de puteri reduse. Intregul proces este monitorizat si controlat de un controller logic programabil PLC in cadrul caruia sunt implementate buclele de reglare (puterea de incalzire SSR si optocuploare, si debit vane bloc reglare combinat).
38
Science and Materials Engineering
S en nc ea an nd dM Ma at er al ng gi ne ee er ng g Sc ci ie ce te ri ia ls sE En in ri in
SPIN DYNAMICS EVIDENCED BY EPR IN Sn1-xMnxO2 NANOPARTICLES ANNEALED AT DIFFERENT TEMPERATURES A. Popa1, D. Toloman1, O. Raita1 , M. Stan1, B. S. Vasile2, L. M. Giurgiu1
National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca, Romania; 2University "Politehnica, Faculty of Applied Chemistry and Material Science, Department of Science and Engineering of Oxide Materials and Nanomaterials 1-7 Gh. Polizu, 011061 Bucharest, Romania, e-mail: popa@itim-cj.ro ABSTRACT
Recently, an intense research activity is being pursued on diluted magnetic semiconductors (DMSs) since the predicted room temperature ferromagnetism in these materials could be useful in spintronics. Tin oxide (SnO2) doped with Mn ions is one of these DMSs where the presence of high-temperature ferromagnetism was reported. It was shown that there is a strong dependence of their magnetic properties on both the sintering temperature and doping content. It is believed that oxygen vacancies and substitutional incorporation are important to produce ferromagnetism in semiconductor oxide doped with transition metal ions. The present paper reports detailed electron paramagnetic resonance investigations (EPR) of the samples in order to investigate the influence of annealing temperature on the properties of Sn1-xMnxO2 powders. X-band and Q-band electron paramagnetic resonance (EPR) studies of Mn2+ ions in Sn1-xMnxO2 powders with x = 0.5%, 1%, annealed at different temperatures is reported. These samples are interesting to investigate as Mn doping produce ferromagnetism in SnO2, making a promising ferromagnetic semiconductor at room temperature.
1
EVIDENCE BY EPR OF FERROMAGNETIC PHASE IN Mn-DOPED ZnO NANOPARTICLES ANNEALED AT DIFFERENT TEMPERATURES D. Toloman1, A. Mezaros2, A. Popa1, O. Raita1, T. D. Silipas1, B. S. Vasile3, A. R. Biris1 And L. M. Giurgiu1
National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca, Romania; 2Technical University of Cluj-Napoca, 28 Memorandumului Street, 400114 Cluj-Napoca, Romania; 3University "Politehnica" from Bucharest, Faculty of Applied Chemistry and Material Science, 1-7 Gh. Polizu Street, 011061, Bucharest, Romania, e-mail: dana.toloman@itim-cj.ro ABSTRACT
This paper reports the influence of the temperature annealing (Ta) on the structural, morphological, Raman and EPR spectra of Zn0.975Mn0.025O nanoparticles. XRD studies reveal a wurzite-type structure, while the formation of ZnMnO3 secondary phase was evidenced only for the nanoparticles annealed at Ta=700 C. This impurity phase was also identified by Raman scattering in the samples thermally treated at 600 C and higher temperatures. EPR investigations show that depending on the annealing temperature, Mn ions are incorporated either in the interior of ZnO nanoparticles (Ta = 425 and 500 C) or at their surfaces (Ta > 500 C). For the sample annealed at Ta= 425 C, a new broad resonance line arises, which was attributed to a ferromagnetic phase. We assume that this ferromagnetic phase could be due to the interaction between the Mn2+ ions and uncompensated acceptor defects incorporated in to the ZnO lattice during the thermal treatment of the samples. Our investigations show that the ferromagnetism in Zn0.975Mn0.025O nanoparticles could appear in the low-temperature annealed samples and disappears in the samples thermally treated at high temperatures. The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 41
1
MAGNETIC RESONANCE INVESTIGATION OF Co2+ IONS IN ZnO NANOPOWDERS M. Stan1, A. Popa1, D. Toloman1, O. Raita1, A. R. Biris2, Ghe. Borodi1, A. S. Biris1, L. M. Giurgiu1
National Institute for Research and Development of Isotopic and Molecular Technologies 400293 Cluj-Napoca, P.O.Box 700, Romania; 2UALR Nanotechnology Center, Applied Science Department, University of Arkansas at Little Rock, Arkansas, 72204, United States, e-mail: manuela.stan@itim-cj.ro
1
ABSTRACT
Magnetic semiconductors, especially TM-doped ZnO, where TM is one of the transitional magnetic elements: Mn, Co, Fe have been of great interest in the last years since they exhibit ferromagnetism with high Curie temperatures above 300K and large magnetization. Electron Paramagnetic Resonance (EPR) spectroscopy is a very sensitive technique for the investigation of the TM ionic states and their local environments and interactions. In the present contribution, we report an EPR investigation of Zn1-xCoxO (x = 0.01, 0.03) nanopowders. Nano-sized powders of Zn1-xCoxO were synthesized by the sol-gel method. X-Ray diffraction studies reveal a wursite- type structure, while the formation of a secondary phase was evidenced by Raman spectroscopy. The morphology and the size of the particles were evaluated by SEM. EPR spectra confirm the substitution of Zn site by Co2+ ions. The EPR parameters of isolated Co2+ ion were evaluated as function of temperature and the doping degree, x. The absence of the hyperfine splitting in our samples could be attributed to an increased number of randomly distributed defects which enhances disorder of the crystalline fields at Co2+ sites.
Zn1-xFexO POWDERS AS SEEN BY EPR O. Raita, A. Popa, D. Toloman, M. Stan and L. M. Giurgiu
National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca, Romania ABSTRACT
ZnO is an attractive system for quite a wide variety practical applications, being a chemically stable oxide semiconductor. It has been shown that Fe doping produces ferromagnetic semiconductor at room temperature [1]. This material, therefore, has the potential for use in spintronic devices such as spin transistors, spin light emiting diodes, very high density nonvolatile semiconductor memory and optical emitters. It is believed that oxygen vacancies and substitutional incorporation are important to produce ferromagnetism in semiconductor oxide doped with transition metal ions. The present paper reports detailed electron paramagnetic resonance investigations (EPR) of the samples in order to investigate how Fe ions are incorporated into the ZnO lattice and their interaction with environment. X-band electron paramagnetic resonance (EPR) studies of Fe3+ ions in Zn1-xFexO powders with X = 1%, 3%, 5% is reported. These samples are interesting to investigate as Fe doping produce ferromagnetism in ZnO, making a promising ferromagnetic semiconductor at room temperature.
[1] S.K.Misra and S.I.Andronenko, Journal of Applied Physics 101, 09H120 (2007)
42
HYBRID MATERIALS OBTAINED BY NICKEL IMMOBILIZATION ON MESOPOROUS MCM-41 AND THEIR APPLICATION IN ALCOHOLS OXIDATION Violeta Niculescu1, Ramona Ene2, Ionut Iordache1, Viorica Parvulescu2
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250.732.744; fax: 0250.732.746; E-mail: violeta@icsi.ro; 2Institute of Physical Chemistry, 202 Spl. Independentei, 060021 Bucharest, Romania
1
ABSTRACT
The mesoporous MCM-41 is successfully used as the support to immobilize transition metals like nickel, both in physical and chemical methods. UV-VIS spectroscopy and N2 adsorption are applied to characterizing these supported catalysts. The results of alcohols oxidation reveal that these supported catalysts have high catalytic activity as their homogenous counterpart does. Keywords: heterogeneous catalysis, MCM-41, mesoporous, nickel catalyst, oxidation.
EXPERIMENTAL RESULTS ON CHEMICAL CLEANING OF FILMED SA106 STEEL L. Popa, M. Tunaru, L. Velciu
Institute for Nuclear Research PO Box78, 1 Cmpului Str., Mioveni 115400, ROMANIA e-mail: laurentiu.popa@nuclear.ro ABSTRACT
The carbon steel components from primary and secondary circuit of a Nuclear Power Station react with high temperature cooling agent forming several iron oxides and oxyhydroxides. These deposits can conduct to some damaging consequences such as: tubes constrictions, pitting and intergranular corrosion and finally to the decreasing of heat transfer and the development of a radiation field around the primary circuit. The cleaning process involves the chemical dissolution of the corrosion deposits in diluted organic acidic solution containing usually a complexing carboxilic acid, a reductant and one or more corrosion inhibitors. To evaluate the removing rates of the superficial films two types of methods were used: gravimetric and potentiodynamic. Correlating our experimental results with literature data, it established the chemical composition of one cleaning solution specific to carbon steels and some other parameters such as: the solution temperature during cleaning process, the contact period of time of sample/ solution and the rapport sample surface/cleaning solution. Finally two models of mechanisms applicable to our specific conditions have been adopted. Keywords: filmed carbon steel, cleaning solutions, gravimetric and potentiodynamic methods
1. INTRODUCTION It is known that corrosion of the mild steel equipments from the secondary circuit can produce thick and adherent deposits which will reduce the heat transfer in this circuit and implicitly will lead to its overheating and failure in severe cases [1].
The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 43
All parts of the secondary circuit can be subjected to corrosion by a variety of mechanisms. Temperature and pH values may be lower in some regions than in others, bringing about the protective oxides on carbon steel surfaces should become lesser stable. In the case of the components subjected at high velocity of fluids are operative the flow assisted corrosion (FAC) mechanisms. In this context, the chemical cleaning of the circuits from the nuclear power plants became very important. The main objective of this operation is the improving of the thermal efficiency by removing of the deposits of corrosion products and oxide films, which hinder the heat transfer through the tube walls and keep the loss of the uncovered metal as small as possible [2]. The heat transfer is influenced both by the compactness degree of the magnetite film and by the fact that the thermal conductivity of magnetite at the operating temperature of a secondary circuit is about 10 times lesser than that of the carbon steels. The presence of a high density of pores could favour the accumulation of steam in pores, which is a poor thermal conductor. The component cleaning is reached using suitable acid solutions and appropriate corrosion inhibitors [3,4]. The cleaning solutions are made usually from mineral acids or mixtures of organic acids, whereas the inhibitors generally consist of a mixture of organic compounds that hinder the corrosion of the uncovered carbon steel by different mechanisms. In this context, it is very useful to control in real time the thermal and chemical stability of the cleaning solution maintaining the solution aggressiveness at a reasonable level. 2. EXPERIMENTAL The material used in our experiments was SA106 gr.B steel having the following chemical composition: 0.09%P, 0.38%Si, 0.01%Al, 0.05%Mn, 0.21%C, 0.05%S and the rest iron. The experiments were made using two types of samples: - uncovered samples mechanically polished, rinsed, degreased in acetone and dried and respectively - filmed samples in autoclaves at high temperature and pressure in AVT solution in conditions specifically to a NPP secondary circuit. To accomplish the paper objective, therefore to try the efficiency of several acid cleaning solutions no inhibited or inhibited, it was necessary to film the samples in the specific conditions of a NPP secondary circuit, namely at (260 5)oC and (5.5 0.5)MPa in a solution prepared using demineralised water treated with volatile amines (AVT) having a pH comprised between 9.4 and 9.7. The filming of the samples was executed in this type of solution in autoclaves at the abovementioned parameters during 90 days. The uninhibited cleaning solutions (D) consisted basically in a diluted solution of citric acid and Na4EDTA having a pH 4.2. The inhibitor introduced in cleaning solutions was triethanolamine (TEA). To establish the inhibitors efficiency, were used comparatively a gravimetric and an electrochemical method potentiodynamic (PD). The protection offered by the inhibitors was evaluated in the case of both methods with the equation:
P(% ) = where:
(corr .rate) abs .inh. (corr .rate) inh. (corr.rate )abs.inh
(1)
(corr.rate)abs.inh.- corrosion rate in absence of inhibitors; (corr.rate)inh.- corrosion rate in presence of inhibitors; P(%) protection (in percents) Electrochemical measurements consisted in potentiodynamic and electrochemical impedance spectroscopy (EIS) methods. These measurements were made using an system constituted from a potentiostat interfaced with a computer. In electrochemical cell were introduced in different cleaning solutions the following three electrodes: the working, auxiliary and reference electrode (SCE).
The main parameters of PD measurements were: - the potential range: [(-250) (+1600)]mV(SCE); - the potential sweep rate: 0.2 mV/sec in the case of filmed samples and 1 mV/sec in the case of bare (uncovered) samples; - the tests were made at two temperatures: the room temperature (255)oC and respectively (805)oC, the last being the usual temperature in the installations during a real execution of cleaning operations. The gravimetric determinations of the corrosion rates consisted in the evaluation of weight losses recorded after cleaning of the filmed samples in presence and respectively in absence of inhibitors. The tests were made at (805)oC in a glass bottle equipped with an upward refrigerant and a magnetic stirrer.
3. RESULTS AND DISCUSSION 3.1. Gravimetric and micrographic results Comparing the experimental weight losses curves corresponding to system uncovered carbon steel/ uninhibited cleaning solution and respectively the same system containing 0.0005M TEA, recorded in static and respectively dynamic regime, we concluded that the values of weight losses recorded in static regime in both situations had been smaller than those recorded in dynamic regime (Figure 1). In Figure 2 are presented the similar curves using filmed samples and an inhibitor concentration of 0.003M (TEA).
0
TD2 uninh. TD6 (0.0005M TEA) Ts13 uninh.
-2
Weight loss (mg/cm2)
-4
Ts15( 0.0005M TEA)

-6
-8
-10
-12 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
time (hours)
Figure 1. The weight loss views corresponding to uncovered SA106 steel descaled in static regime in uninhibited solution (Ts13) and respectively with 0.0005M TEA (Ts15) and in dynamic regime in similar conditions (TD2, TD6)
45
SA 106 F-T13 SA 106 F-T11
0
SA 106 F-TD2 SA 106 F-TD8
-2
Weight loss (mg/cm2)
-4
-6
-8
-10
-12 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
time (hours)
Figure 2. The weight loss views corresponding to filmed SA106 steel descaled in static regime in uninhibited solution (T13) and respectively with 0.003M TEA (T11) and in dynamic regime in similar solutions (TD2 and TD8)
Representing in Figure 3 the weight losses data recorded in static regime corresponding to systems filmed samples/ solutions containing some increasing concentrations of TEA, we remarked that: - the greatest values of weight losses were recorded in uninhibited solutions; - with the increasing of TEA concentration added in cleaning solution, - the corresponding values of weight losses had been smaller and smaller. Representing the similar values recorded in other case in dynamic regime, we remarked a similar tendency of kinetic curves, only difference consisting in the greater values recorded. The films formed after 90 days of autoclavization in AVT solution at parameters specifically to secondary circuit had a thickness comprised between 3 and 8 m, being relatively uniform and continuous. After 2 hours cleaning in static regime, was ascertained a great thinning of film, while after a dynamic cleaning of one hour, we observed that the film is completely removed ( Figure 4).
SA 106 F-T10
0
SA 106 F-T11 SA 106 F-T13
SA 106 F-T12 Weight loss (mg/cm2)

-1
SA 106 F-T15
-2
-3
-4
-5
-6 0 0. 5 1 1. 5 2 2. 5 3 3. 5 4 4. 5
tim e (hours)
Figure 3. The weight loss views corresponding to filmed SA106 steel descaled in static regime in uninhibited solution (T13) and respectively containing following TEA concentrations: 0.0005 M (T15), 0.00113 M (T10), 0.0045 M (T11), 0.0083 M (T12)
a)
b)
c)
Figure 4. Micrographies of SA106 steel samples: a) filmed by autoclavization; b) remanent film after one hour of descaling in dynamic regime; c) remanent film after two hours of descaling in dynamic regime 3.2. Electrochemical results Applying at 25C the potentiodynamic method to systems formed from two kinds of samples/ uninhibited cleaning solutions, we observed: the value of Ecorr corresponding to filmed samples was with max.200mV nobler comparatively with the similar value corresponding to uncovered (bare) samples; the values of corrosion rates of filmed samples were lesser 2.53 times than the similar values corresponding to uncovered samples. Comparing the behaviour of the same system: filmed samples/uninhibited cleaning solution at two temperatures: 25C and 85C, it remarked an acceleration of corrosion with the increasing of temperatures. On the basis of literature data and our experience, we remarked that: the presence of an increased concentration of any efficient inhibitor conducted at the parallel displacement of cathodic and anodic Tafel lines. These results indicated that the inhibitor present in solution inhibited both the hydrogen evolution and the dissolution process, proving that this compound acted as mixed-type inhibitor. the better inhibitor the greater displacement of cathodic and anodic Tafel lines. Starting from above-mentioned electrochemical findings and considering also the values included in Table 1, we exhibit down the main data referring to the inhibitors studied. In this Table are presented the electrochemical rates calculated on the basis of Tafel slopes (c, a) and polarization resistance (Rp) in view to estimate the efficiency of inhibitors.
a)
b)
Figure 5 a, b. The PD diagrams corresponding to systems formed from filmed (a) and respectively uncovered samples (b)/ uninhibited solution (D) (curves 2a, 1b ) and respectively/ (D+0.003M TEA) (curves 1a, 2b)
Therefore, the cleaning of filmed samples of three carbon steels types which proceeded at 85C, executed in presence of several concentrations of triethanolamine (TEA) shown that the most spectacular results were obtained in presence of 0.003M TEA (Figure 5a, b). Examining the two Tafel lines (cathodic and anodic, respectively) corresponding to the behaviour of the system: filmed
samples/ (solution + inhibitor) respectively solution no inhibited, it observes a displacement almost parallel of both lines; this fact indicates that TEA is a mixed-type inhibitor. Experience has shown that as long as there is a galvanic coupling between magnetite and base metal, the magnetite dissolution proceeds through a chemical reaction having an electrochemical path, where magnetite reduction and metal oxidation support the cathodic and anodic processes respectively. From this standpoint, the removal of magnetite film is carried out by the overall reaction: Fe3O4 + Fe + 8 H+ 4 Fe2+ + 4 H2O (2)
This reaction shows that the direct oxidation of the base metal is an essential step. This observation means that ferric ions do not play a main role as concerns the corrosion of carbon and low-alloyed steels because, as a consequence of the reaction (2), Fe3+ ions mainly come from the oxidation of Fe2+ and are present at small concentrations. Furthermore, other minor source of Fe3+ ions is represented by the chemical dissolution of small scales of magnetite in the solution bulk. Thus, the overall reaction: Fe + 2 Fe3+ 3 Fe2+ (3)
has only a negligible effect on the stability of base materials. Other important consequence of the reaction (2) is that a corrosion inhibitor must not hinder her kinetics, otherwise the complete magnetite dissolution could take a long time. Therefore, the main role of corrosion inhibitors added to acid cleaning solutions is to restrain the corrosive attack on the bare metal. The free dissolution rate increases with the concentration of H+, Fe2+ and decelerates with the increase of Fe3+ concentration. The same rate increases with the increase of FeII in the surface lattice; this fact is accomplished by a reductive agent, by the preparation mode of the oxide or by a catalytic effect of Fe2+ in solution, being considered that it promotes an electron exchange with FeIII from the crystal lattice. The decrease of the dissolution current with the cathodic polarization after the reach of the first maximum is explained by enrichment of the oxide surface in cations5,6. In the case of use for cleaning of chelating agents, the maximum rate of dissolution is at pH = 2.22.6, when the stability constant of FeIII complex is high. The dissolution starts with the adsorption and attack of the chelating anion at the surface iron sites, followed by the complexation and dissolution. Some authors reported that the dissolution efficiency decreases in the order: EDTA> oxalic acid> nitriloacetic acid> ascorbic acid> citric acid1.
Table 1. Electrochemical parameters corresponding to systems filmed SA106 carbon steel / several cleaning solutions Electrochemical parameters determined from System studied PD curves Rp E(I=O) Vcor a c [mV] [V/dec] [V/dec] [mpy] [ ] -280,3 100 100 80,84 41,36 SA 106 F/T 13 (uninhibited solution - D) SA 106 F/ T 10 -291,6 100 100 59,05 56,62 (D+0,00113M TEA) SA 106 F/ T 15 -318,5 100 100 70,86 47,19 (D+ 0,0005M TEA) SA 106 F/ T 11 -303.5 100 100 25.37 131.8 (D+0,003M TEA)
Curve PD 5 PD 6 PD 7 PD 8
If is considered that the magnetite film formed over carbon steel surfaces at the high temperature and pressure, under reducing and alkaline conditions is a protective layer with low
defect concentration, is clear that the transportation of ions through the pores in the oxide and along the oxide grain boundary is very important. When this magnetite-coated carbon steel is exposed in organic acids and a complexing agent, the magnetite film is progressively dissolved followed by complexation of iron ions. The carbon steel base metal, in the absence of magnetite film, has been found to undergo some corrosion by the anodic dissolution of the metal due to acid present in medium. The wall thinning taking place in the absence of magnetite film, can be accurately quantified by simple methods such as weight loss or electrochemical methods. But a quantification of wall thinning that takes place when the magnetite film undergoes dissolution is difficult. A possible method is the determination of iron concentration from cleaning solution simultaneously with the determination of hydrogen volume released. The explication of great efficiency of TEA consists in the presence of three OH- groups in this inhibitor. These OH- groups having a polar character, easily are adsorbed on the surface of samples covered with iron oxides and respectively oxy-hydroxides. Afterwards, TEA adsorbed molecules easier changes out of place the water molecules from the superficial film, forming several complexes with the superficial iron oxides. In this way this process will lead, finally, at the diminution of corrosive attack of solution ions. It is known that the corrosion inhibitors contain hydrophile or hydrophobe groups. In the presence of the wet surfaces of samples, it is very probable that the both components of the system the superficial oxide and the solution - should attract the hydrophile groups. Several studies shown that the dispersible inhibitor solutions under form of stable emulsions where the inhibitor concentrations are more or at least equally with the critic micelle concentration (CMC), are more efficient than the solutions where their concentration is placed under CMC value. It is known that the variations in the chemical composition of the inhibitors may attract great changes in their performances. Consequently, were been executed a lot of studies which followed the correlation of the molecular structure of several types of inhibitors with their efficiencies7. When the corrosion inhibitor is in the proximity of the metallic surface, it is important to establish which functional groups will tie with the metal, the strength of these links, which functional groups contribute at the formation of the superficial films and the modality in which the chemical new formed bonds may affect the resistance of this new formed film.
Figure 6 [4] Illustration of the possible amine adsorption mechanisms: a) chemisorptions on the metal surface and b) hydrogen bonding to the superficial passive film
The inhibitors type amine containing two or more amine groups in their molecules, are more efficient in identical concentrations than the homologue substances that contain one amine group. The arylic inhibitors which contain amine and thio-groups bound from the benzenic nucleus, may adsorb on the metals; after that, function of their molecular constitution, may change especially the cathodic process mechanisms by formation of some corrosion products which will participate
afterwards at the formation of the superficial films. Some researchers studying this phenomenon established that the organic inhibitors containing diamines might produce several configurations or orientations function of several adsorption possibilities on the metallic surface (Figure 6).
CONCLUSIONS
1) To evaluate the efficiency of uninhibited and respectively inhibited cleaning solutions, we used the gravimetric and potentiodynamic methods applied in parallel to the filmed and respectively bare samples of carbon steel SA106. In the same goal, tests in cleaning uninhibited solutions and respectively in the same solutions containing several concentrations of triethanolamine as inhibitor were executed. This inhibitor was used in the following concentration range: [(5.10-4)(2.10-2)]M. 2) Metallic corrosion in aqueous acid solutions being a complex and heterogeneous process, the inhibitor existing in these solutions will interact with anodic and cathodic surface reaction sites, either retarding the electrochemical reactions or limiting the transport of reactive corrosive species from solution. 3) The most rapid method of comparing of the efficiency of inhibitors was proved the superimposing of cathodic region of PD curves. 4) The explication of great efficiency of TEA consists in the presence of three OH- groups in this inhibitor that having a polar character, easily are adsorbed on the wet surface of samples covered with iron oxides and respectively oxy-hydroxides.
REFERENCES
1. 2. 3. 4.
Prince A.A.M., Journal of Nuclear Materials, 2001, 289, 281-290; Velmurugan S., Rufus A.L., Nuclear Energy, 1995, 34, 103-110; Blesa M. A., Borghi E. B., J. Colloid Interface Sci., 1984, 2, 295-308; Godfrey, M. R.Chen, T. Y., Corrosion NACE, 1995, 51, 797-805.
EVALUATION OF PHISICAL STABILITY OF THE U-ZrH SYSTEM Mariea Gruia (Deaconu)1, Ion Ciuca2, Marioara Abrudeanu3, Tiberiu Meleg1, Iulia Dumitrescu1
1
RAAN -Institute for Nuclear Research, Pitesti - Mioveni, Romania, e-mail: mariea.deaconu@nuclear.ro; 2 University POLITEHNICA of Bucharest; 3University of Pitesti, Romani
ABSTRACT
The physical stability of uranium zirconium-hydride fuel has been studied by means of simultaneous measurements of thermo-gravimetric and differential thermal analyses (TGA-DTA). The uranium-zirconium fuel is an integral fuel-moderator system and the fuel manufactory technologies are based on powder metallurgy. The experimental studies consisted in thermal cycling tests on uranium-zirconium hydride (45 wt% uranium) fuel over the temperature range 500 to 750C. During thermo-gravimetric research, we noticed mass los and the thermal events occurring (the phase transformation) to the sample are recorded by DTA. Morphological and structural changes were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM) after 100 heating-cooling cycles. The purpose of this paper is to describe the experimental data which supplies the information regarding the practical use of TRIGA fuel elements, fabricated at INR. 50 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
S en nc ea an nd dM Ma at er al ng gi ne ee er ng g Sc ci ie ce te ri ia ls sE En in ri in Keywords: Thermal cycling, uranium zirconium hydride, thermo-gravimetric
BEHAVIOUR EVALUATION OF SOME STRUCTURAL MATERIALS FOR HEAVY WATER PLANT EXPOSED TO SULPHURETTED HYDROGEN ENVIRONMENT Lucian Velciu, Maria Mihalache, Al. Niu, Laureniu Popa, Alice Dinu
Institute for Nuclear Research Piteti,Cmpului Street, No. 1, Mioveni, Arge, Romnia PO BOX 78, 1 Campului Str. Mioveni, 115400, E-mail: Lucian.velciu@nuclear.ro
ABSTRACT
This paper aim is to present the metallographic analysis performed on some structural materials liable to action of sulphuretted hydrogen environment, different time periods. Were examinate two metallic materials: carbon steel and stainless steel (G52-28 and 304L) tested in GS1 column of ROMAG-PROD Heavy Water Plant and in an experimental installation developed by ICSI Rmnicu-Vlcea. The samples were maintained in sulphuretted hydrogen environment for a time period comprised between one month and about 2.5 years. Some of the tested samples were protected by different layers (pyrite, ceramics or metallic deposit) and the others were not protected. The evaluation of materials behaviour was performed using the metallographic methods, chemical elements determination (hydrogen content) and microhardness test. The analysis consisted in the evaluation of the quality of the structural materials and layers formed, after exposed period, using the optic and electron microscopy. In conclusion was observed that the samples protected by different layers were less affected than the unprotected samples. The exposure time is also important: a large period leads to a negative impact especially for the carbon steel. Keywords: carbon steel, stainless steel, sulphuretted hydrogen, microstructure, microhardness.
INTRODUCTION
This paper examined the action of hydrogen sulphide (H2S) on some metallic materials used in building of installations of heavy water production. A convenient method to obtain the heavy water by ordinary water, used in Romania at ROMAG-Prod Drobeta Turnu-Severin, is the hydrosulphurous proceeding called Girdler-Sulphide (GS). In this installation of heavy water production is used carbon steel type G 52-28. Although this steel reacts easily at sulphuretted hydrogen, it is used in building of installations because requiring very big quantity it is an economic material as against another [1], [2]. The contact of liquid and gaseous fazes circulated in counter-current is realized by some elements of contact (disks) made of stainless steels. In many materials the presence of hydrogen have a brittleness effect, especially on those whit superiors mechanical proprieties. Another effect is that of crack determined of mono-atomic hydrogen which proceeds from generalized corrosion (cathode reaction) or from hydrogen in solution adsorbed on metal surface. Because at low temperature hydrogen no more diffused, remained in crystalline cell metal, caused the stress which favour the cracking. A protective method for the interior surface columns of installation against the corrosion products deposits is achieved by the chemical passivity (controlled attack of surface) whit form an impermeable layer for H2S. Because the layer formed has of a majority the pyrite compound, the proceeding is named pyritization.
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EXPERIMENTAL METHODS
Were exanimate two metallic materials: a carbon steel (G52-28) and a stainless steel (304L) which were exposed in GS1 (hot-cold bithermal) column from ROMAG-Prod Heavy Water Plant [1],[2] and in an experimental installation developed by ICSI Rmnicu-Vlcea [3]. The samples were maintained in sulphuretted hydrogen environment for a time period comprised between one month and about 2.5 years. Some of the tested samples were protected by different layers (pyrite, ceramics or metallic deposit) and the others were not protected. The usual methods for examination were: optic and electron microscopy (metallography), chemical elements determination (hydrogen content) and micro hardness test. The origin samples and notations: 1. Samples from ROMAG. Aspiration pumps (P): 682-P1303C, 761-P1304C, 653-P1308; Cold column: C1103B-GS1column, notation CC or PC: Inox-CC, PC3, PC10; Hot column: C1104B-GS1, notation HC or PH: Inox-HC, PH3, and PH10. 2. Samples from ICSI Rm. Vlcea. Samples whit stainless steel deposition: A12 (720 hours pyritization) and B11(720 hours pyritization + 2358 hours tested); Sample whit ZrO2 deposition: E11(720 hours pyritization) and E2 (720 hours pyritization +2358 hours tested), where 720 hours is pyritization time and 2358 hours-tested time in H2O-H2S medium. The samples were stamped for identification: A, B, C- Samples whit stainless steel deposition (308L) and followed of pyritization; D, E, F- Samples whit ZrO2 deposition and followed of pyritization. 3. As received samples (witness). Carbon steel G52-28, notation: M-OLC; Stainless steel (304L/316L), notation: M-Inox Test conditions: The ROMAG samples were tested even in the installation of heavy water production (GS1 column) on her exploitation period (about 2.5 years): hot column temperature 127-137C and pressure 1,96-2,06 MPa; cold column temperature 32-35C and pressure 1,9-2,0 MPa. The ICSI samples were tested in an experimental installation developed by ICSI RmnicuVlcea, the test conditions being presented in Table 1.
Table 1. Test conditions, ICSI: H2O- H2S, [2]
Parameters Pressure Temperature Working medium H 2 S Water saturation H 2 S Composition Flow (water + H 2 S) Exposure/test time Stop times (revisions)
RESULTS AND DISCUSSION
UM bar C % % m3/h hour hour
Values 10-21 30-135 H2O-H2S; H2 moist 3,5-4,5 Min.99,8 1,5-7,5 2304 54
Metallographic analysis, [3] Metallographic analysis were performed visual for macroscopic examination (photographs by camera) and by optic microscopy for microstructure. After the preparation of metallographic samples (cutting, polishing, etching), the microscopic examination of structure were performed using a metallographic microscope type Olympus GX 71 (magnification x50-x200). Macrostructure (visual examination), [3] Figure 1 - Carbon steel sample (type G52-28), as received (witness). The macrostructure aspect of the samples exposed in cold column (CC):
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Figure 2 - Plate with instable dust deposit in superficial layer, easily separate at manipulation. The macro structural aspect of the samples expose/maintain in hot column (HC): Figure 3 - Plate with adherent deposits (relative) and non-uniform corrosion zones.
Figure 1. As received sample, G52-28
Figure 2. G52-28, CC, after testing
Figure. 3. G52-28, HC, after testing
Microstructure, [3] The etching reactive used were: chemical etch whit nital (2%) for carbon steel; electrolytic etch whit 10% solution oxalic acid, 6V, for stainless steel. Carbon steel (G52-28): Figure 4. Carbon steel, as received: Ferrito-pearlitic structure with pearlite (dark rows) rifed in ferrite mass (blank).
Figure 4. Carbon steel, as received sample: ferrite+pearlite
Figure 5- Carbon steel, HC sample: ferrite+pearlite
Figure 6- Carbon steel, CC sample: ferrite+pearlite
Figures 5-6. The carbon steel samples from the two columns present a similar microstructure: Ferrite+Pearlite with pearlite rifed in ferrite mass. Stainless steel (304L): Figure 7 - Stainless steel, as received: austenitic structure with twined grains and carbides precipitates. Figures 8-9. The stainless steel samples from the two columns present a similar microstructure: austenitic structure with twined grains and carbides precipitates.
Figure 7. Stainless steel, as received sample: austenite+carbides
Figure 8. Stainless steel, HC Figure 9. Stainless steel, CC sample: austenite+carbides sample: austenite+carbides
Electron microscopy (SEM), [3] The study of the base material and the zone near the formed layers (iron pyrites) were realized with the electron microscope of high resolution TESCAN VEGA II LMU. Carbon steel G52-28 samples:
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Figure 10 - Hot column (HC), carbon steel: micro-cracks (x2000), porous layer +compact; crakes in layer (x250). Figure 11 - Cold column (CC), carbon steel: porous external layer+internal homogeneous, nonuniform+corrozive penetration in substrate.
Figure 10. HC carbon steel: micro-cracks, porous layer+compact
Figure 11. CC carbon steel: porous external layer+corrozive penetration in substrate
Stainless steel samples: Figure 12 - CC stainless steel, thickness layer 35-38 m (centre)+unaffected base material (right-bottom); Figure 13 - HC stainless steel, thickness layer 25 m (centre)+unaffected base material (right-bottom).
Figure 12. CC stainless steel, thickness layer 35-38 m (centre)
Figure 13. HC stainless steel, thickness layer 25 m (centre)
To notice that in the same test conditions, the carbon steel samples were very corroded comparatively with stainless steel samples which not have significantly modifications.
Hydrogen content (hc), [3] The hydrogen content determination were realized with ELTRA OH 900 analyzer. From the samples (witness and tested) were cutting pieces of 0.2-0.4 grams which then were descaling and weighing. The result of determinations is presented in Table 2. To notice an increment of hydrogen content on unprotect samples comparatively with as received samples. Also, comparative with hot column, in the experimental conditions of cold column, it was observed a higher absorption of hydrogen on the unprotected samples. In general, the pyritized samples present a hydrogen content (ch) comparable with as received samples. The sample of cold column (30C) have a hydrogen content (ch=2.99-3.03 ppm) higher about 2.5 time given the hot column (130C) samples (ch=1.13-1.44 ppm). This thing it happen because at low temperature hydrogen no more diffused, remaining in metal.
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Table 2. Hydrogen content, [3]
No. crt. 1 2 3 4 5 6 7 8 9 10
Material Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Stainless steel Stainless steel Stainless steel
State/ Test/ Origin as received Cold column -ROMAG Hot column-ROMAG Pump P1303C-ROMAG Pump P1304C-ROMAG 720 h / ICSI 720+2358 h / ICSI as received Cold column -ROMAG Hot column -ROMAG
Hydrogen content, hc [ppm] 0.13 2.99-3.03 1.13-1.44 0.65 2.99 0.32 0.44 0.78 1.90 0.81
In conclusion on remark that the pre-filmed material with the protective layers reducing the hydrogen adsorption in base metal.
Microhardness tests (Vickers), [3] The determinations of Vickers micro hardness were performed on samples in cross section using a (micro) durometer OPL (x500). After microstructure etch, the Vickers micro-hardness tests were performed at 0.1 Kgf (100gf) micro-load and were obtained following average values presented in Table 3 [3]: Table 3. Microhardness Vickers (MHV0,1) Microhardness, MHV 0.1 [kgf/mm2] Material, sample code Interface strate/substrate Central zone Carbon steel, as received 170 Cold column-CC 170 147-159 Hot column-HC 161 156 Pump-P1303/1304 141-181 151-165 A12, 720h ICSI 181 158 E2, 720+2358h - ICSI 193 158 Stainless steel, as received 185 Stainless steel, Inox-CC 175,5 170 Stainless steel, Inox-HC 210 186
No. crt. 1 2 3 4 5 6 7 8 9
After experiments on comes a diminution of the microhardness of tested samples comparative with as received sample in central zone and a growth in the state/substrate interface.
CONCLUSIONS Macrostructure: The samples on cold column presented an instable dust deposit; the sample on hot column presented an adherent deposits and non-uniform corrosion zones. Microstructure: The carbon steel samples from the two columns present a similar microstructure: Ferrite+Pearlite with pearlite rife in ferrite mass. The stainless steel samples from the two columns present a similar microstructure: austenitic structure with twined grains and carbides precipitates. Electron microscopy (SEM): In the same test conditions, the carbon steel samples were very corroded comparatively with stainless steel samples which not have significantly modifications.
Hydrogen content (hc): After tests, the hydrogen content on unprotect samples growth comparatively with as received samples. Also, comparative with hot column in the cold column, it was observed a higher absorption of hydrogen on the unprotected samples. Also, the pre-filmed material with the protective layers reducing the hydrogen adsorption in base metal. Vickers microhardness: After experiments, on comes a diminution of the microhardness of tested samples comparative with as received sample in central zone and a growth in the state/substrate interface. Influence of sulphuretted hydrogen environment: was observed that the samples protected by different layers were less affected than the unprotected samples. The exposure time is also important: a large period leads to a negative impact especially for the carbon steel. REFERENCES
[1] L.Velciu, A. Dinu, D. Doanta -Examinarea otelului G52-28 expus in coloanele de schimb izotopic- R.I nr.77xx/2007-S.C.N-Pitesti, 2007 [2] A.Deaconu, V.Pitigoi, L.Velciu, F.Voicu- Supravegherea proprietatilor fizice si chimice ale materialelor de structura si ale stratului piritizat- RI nr. 64xx/2002 S.C.N.-Pitesti, 2002 [3] L.Velciu, A. Dinu, M. Mihalache, M. Dragomir Evaluarea comportrii n timp a materialelor structurale care func ioneaz n mediu de hidrogen sulfurat- R I nr. 93xx/2011 S.C.N.-Pitesti, 2011
INVESTIGATED OF TUNGSTEN-LEAD-BORATE GLASSES BEFORE AND AFTER LASER IRRADIATION M. Rada1, E. Culea2, N. Aldea1, S. Rada2, V. Rednic1, A. Bot1, D. Silipas1
2
National Institute for R&D of Isotopic and Molecular Technologies, Cluj-Napoca, 400293, Romania Department of Physics&Chemistry, Technical University of Cluj-Napoca, 400020 Cluj-Napoca, Romania
ABSTRACT
Glasses in the xWO3(100x)[3B2O3PbO] system, where 0x40 mol%, are obtained by conventional meltingquenching method and characterized using X-ray diffraction, FTIR spectroscopy and DFT calculations. These tungstenleadborate systems exhibit a photochromic effect which can be induced through laser exposures (=633 nm) directly on the bulk sample. Structural investigations show that the photosensitive effect are due to a reduction of W+6 to W+5 and/or W+4 promoted by the oxidation of Pb+4 and some structural changes of the borate network. DFT calculations show higher thermodynamic stability of the [W2O7] and [WO4] polyhedrons comparative with the [WO6] polyhedron.
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PLATINUM BASED MULTI-SHELL MAGNETIC NANOPARTICLES AND FUNCTIONALIZED COMPOSITES O. Pana1, C. Bele2, S. C. Matea2, M. L. Soran1, C. Leostean1, M. Stefan1, S. Macavei1
1
National Institute for R&D of Isotopic and Molecular Technologies, P. O. Box 700, 400293 Cluj-Napoca, Romania; 2University of Agricultural Sciences and Veterinary Medicine Cluj-Napoca, Romania
ABSTRACT
In the present work the following systems were prepared and characterized: core-shell iron / platinum nanoparticles, (Fe@Pt), and La0.67Sr0.33MnO3 (LSMO) manganite nanoparticles covered with platinum (LSMO@Pt). The Fe@Pt nanoparticles were prepared by the reverse micelle method. First the iron cores were realized by using cetyltrimethylammonium bromide as surfactant. In the second stage, starting from K2PtCl6, in 1-butanol and octane, the Pt shell was added. In case of LSMO@Pt nanoparticles the LSMO cores were prepared by using a sol-gel method followed by Pt shell formation by a seeding method. In view of further bio-applications, in the thirst stage, the nanoparticles were covered with an additional silica shell. The process was realized by using a Stber system resulted by mixing ethanol, ammonium hydroxide, H2O and triethylorthosilicate (TEOS). In order to conjugate BSA-FITC onto the outer shell of nanoparticles 3-aminopropyltrimethoxysilane was used. Finally bovine serum albumine fluorescein isothiocyanate was covalently bound to the multi-shell system. Luminescent response of water dispersed nanoparticles was investigated by confocal microscopy. The properties of the composites were investigated by TEM, HRTEM, XRD and XPS. Also, SQUID and VSM techniques were used to study the magnetic properties of the as prepared functionalized multi-shell systems.
GLYCEROL HYDROGENOLYSIS OF GLYCEROL TO PROPYLENE GLYCOL ON COMMERCIAL NICKEL CATALYSTS DESCRIBED BY A MATHEMATICAL MODEL Adriana Marinoiu1, Elena Carcadea1, Catalin Capris1, Claudia Cobzaru2, Vasile Tanislav1, Iordache Ioan1
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm Valcea, 4 Uzinei St., Rm Valcea, Romania; 2Gh. Asachi Technical University of Iai, Faculty of Chemical Engineering and Environmental Protection, D. Mangeron, 71, 70050
1
ABSTRACT
Bio-diesel is produced using alcoholysis of bio-renewable fats and oils. From each unit of vegetable oil that is converted to bio-diesel approximately 10% by weight will be recovered as by-product glycerol. The bio-diesel production increasing will lead to large quantities of glycerine. The commercial propylene glycol production route is propylene-based, through propylene oxide, and therefore it is connected to the price of petroleum. Utilizing the glycerol, not only would help the decreasing of bio-diesel production, but the inexpensive propylene glycol could be used as a low- toxicity replacement for ethylene glycol. The creating a low-cost catalytic process for converting the glycerol, a by-product from bio-diesel production, in propylene glycol, could have a major impact on the future use of bio-diesel fuel. In our study, glycerol is reacted over a heterogeneous catalyst with hydrogen at moderate conditions. Reactions were conducted in following conditions: temperature 180-2200C, reaction pressure in range 8-30 bar, reaction time 8 hours. The activation of the catalysts was performed simultaneously with the hydrogenation at temperature in range 200-2500C, and reaction time for 2-4 hours. The conversion of glycerol hydrogenolysis in aqueous solutions on a commercial nickel catalyst is evaluated under various conditions of temperature and time. These parameters are necessary and sufficient for developing a The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 57
S en nc ea an nd dM Ma at er al ng gi ne ee er ng g Sc ci ie ce te ri ia ls sE En in ri in mathematical model of the hydrogenolysis process. The number of equations decreases very much and the equation corresponding to the best mathematical model is finally obtained. Three equations specific to the hydrogenation process and the correlation coefficients were presented. The mathematical model developed using Table Curve 3D software program for the hydrogenation process over the nickel catalyst has the correlation coefficient closed to unity. The characteristic equation of this model describes the dependence of the hydrogenation process conversion on the temperature and time. Keywords: copper chromite catalyst, hydrogenolysis, mathematical model
EFFECT OF DISPERSION SOLVENT IN CATALYST INK FOR MEMBRANE ELECTRODE ASSEMBLIES Adriana Marinoiu, Irina Petreanu, Laurentiu Patularu, Mircea Raceanu, Amalia Soare
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, 4 Uzinei St., Rm Valcea, Romania
ABSTRACT
Fuel cell systems offer the promise of economically delivering power with environmental and other benefits. The membrane electrode assembly (MEA) is the key component of the fuel cell. The deposition of the right catalyst content on the electrodes by a simple method is desirable in the effective production of MEA. The effect of dispersion solvents in catalyst ink on performance of structural catalyst layer is studied. In this study a precursor ink composition is developed to produce high performance catalyst layers. The control of the surface tension of the catalyst ink is fundamental to allow the catalyst layer deposition by spraying technique and an optimal ink composition was studied. Different catalyst inks with various solvents (methanol, glycerol, 2-propanol, and ethanol) were prepared and the effect of dispersion solvent was discussed. The prepared CCM (catalyzed coated membrane) were observed under scanning electron microscope (SEM) to examine its morphology: the thickness and uniformity of the catalyst layer. Proper dispersion of Nafion ionomer and catalyst particle is one of the critical factors for CCM obtaining and catalyst utilization. Micro structural characterization was carried out in connection with the prepared CCM and from EDS examination, elemental map analysis was obtained for all the elements present in the catalyst layer. Ink containing high boiling point solvents (such as glycerine) had less cracks than inks containing a low boiling point solvent, such as methanol. The explanation is: the low boiling point solvent evaporated much faster than the high boiling point solvent during the coating of the catalyst ink. High drying speed caused surface cracks. The catalyst ink containing iso-propanol had better dispersion and proved a uniformity of the catalyst layer. The efficiency of CCM made from iso-propanol solvent is attributed to aggregated ionomer that created large pores for fast mass transfer and better proton conducting network in the catalyst layer than those created by solution phase ionomer. Additional studies regarding other methods for improving the performance of the membrane electrode assembly due to catalyst ink are currently under investigation.
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Nuclear Power fission and fusion
N Nu uc ea ar Po er na an nd df us n cl le rP ow we r f fi is ss si io on fu si io on
GENERATION IV NUCLEAR ENERGY SYSTEMS OVERVIEW Ramona-Maria Voiculescu*, Viorica-Maria Nistor, Marius Olteanu
Institute for Nuclear Research, Campului Street, 1, Mioveni, 115400, Romania, Phone: +40248213400, Fax: +40248262449; * INRs Reliability and Testing Laboratory, Phone: +40248213400, Extension: 130, E-mail: ramona.mihaiu@nuclear.ro
ABSTRACT Taking into account the expected increase in energy demand worldwide and the growing awareness about global warming, climate change issues and sustainable development, nuclear energy will be needed to meet future global energy demand. For these reasons and others, the purpose of the GIF-Generation IV International Forum and the vision for Generation IV were defined in Charter of the Generation IV International Forum: the development of concepts for one or more Generation IV nuclear energy systems that can be licensed, constructed, and operated in a manner that will provide a competitively priced and reliable supply of energy to the country where such systems are deployed, while satisfactorily addressing nuclear safety, waste, proliferation and public perception concerns. The paper aims to summarize the reasons that led to R&D (Research&Development) of next generation of nuclear energy systems, to present the GIF (GIF Charter, Framework Agreement, Structure, Responsibilities and Members) and to describe all nuclear energy systems (Gas-Cooled Fast Reactor System, Lead-Cooled Fast Reactor System, Molten Salt Reactor System, Sodium-Cooled Fast Reactor System, Supercritical-Water-Cooled Reactor System, Very-High-Temperature Reactor System) chosen by GIF for future R&D. Also, the paper will present the Romanian position related to the participation in R&D of next generation of nuclear energy systems. Keywords: generation IV, international forum, innovative nuclear energy systems
INTRODUCTION For the earth to support its population (which is expected to expand from 7 billion people today to over 9 billion people by the year 2050) we must increase the use of energy supplies that are clean, safe and cost effective. On the other hand the importance of reducing emissions is vital, so many strategies and scenarios are proposed in order to achieve more sustainable future energy supplies. Prominent among these supplies is nuclear energy. There is currently 370 GWe of nuclear power capacity in operation around the world, producing Figure 1. World Nuclear Reactor Fleet, 19542011 3000 TWh each year (15% of the worlds (Source: IAEA-PRIS, MSC, 2011)[1] electricity), the largest share provided by any non-greenhouse gas-emitting source. However challenges still exist to long-term deployment of nuclear. Firstly, nuclear energy must become more sustainable in its utilisation of uranium or thorium ores, as well as the management and disposal of nuclear waste. Secondly, nuclear plant must be economically competitive, yet their safety must remain of paramount importance. Additionally, deployment of
N Nu uc ea ar Po er na an nd df us n cl le rP ow we r fi is ss si io on fu si io on f
nuclear plant must be undertaken in a manner that can guarantee worldwide non-proliferation of nuclear weapons. Finally, some plants should help to meet anticipated future needs for a broad range of energy products beyond electricity. Generation IV nuclear energy systems are aimed to meet these challenges by delivering unprecedented performance. Given all this, the paper shall present the reasons leading to the need for a next step in nuclear reactors (that can be divided historically, into generations), the Generation IV International Forum mission and the innovative nuclear energy systems chosen by GIF for future R&D. Also, Romanian point of view, related to the national strategy and INR involvement in GEN IV, will be pointed. 1. Reasons for a new era in nuclear Population growth and economic development are the main drivers that lead to increased energy consumption and so it is clear that energy demand will continue to increase for many decades to come as emerging and developing countries strive for improved standards of health and greater prosperity. Regarding to this, the expected global growth of nuclear energy covers a wide range:
Figure 2. Range of expected nuclear power capacity in SRES* scenarios, 2000-2050. (Solid line represents median) [2] The need of increasing the energy supplies is obvious (from the point of view of population growth) but at the same time the importance of reducing greenhouse gas emissions is now universally recognized. In the majority of these, the prospects are good for nuclear energys growth. Nuclear power plants do not produce global warming [3] emissions when they operate, and the emissions associated with the nuclear fuel cycle and plant construction are quite modest (and will fall further if industry and transportation rely less on fossil fuels). For example, the 2008 World Energy Outlook forecasts an additional 250 GWe of nuclear capacity by 2030 in a scenario that would stabilize the atmosphere at 450 ppm CO2 and thereby limit global warming to 20C above preindustrial levels. [4] Another reason for R&D of GEN IV is that the world is now approaching to the end of the first era of nuclear power. Most of the reactors built in the past several decades are still operating, and many will continue to run for a number of additional decades but a large number of these plants are at or near the end of their operating licenses. So, gradually the existing reactors will be shut down, and the number of commitments for further reactors is relatively small (details can be seen in
SRES Special Report On Emission Scenarios The terminology nuclear eras has been used by a number of authors, notably by Alvin Weinberg in his papers: A.M. Weinberg and I. Spiewak, Inherently Safe Reactors and a Second Nuclear Era, Science 224, 1984: 13981402 and A.M. Weinberg, I. Spiewak, J.N. Barkenbus, R.S. Livingston, and D.L. Phung, The Second Nuclear Era: A New Start for Nuclear Power, New York: Praeger, 1985 62 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
figure no. 3). For that reason substantial efforts are underway to develop next generation reactors that would usher in a Second Nuclear Era. [5] In the latter part of this century, the environmental benefits of nuclear energy can expand and even extend to other energy products besides electricity. For example, nuclear energy can be used to generate hydrogen for use in petroleum refinement and as a transportation fuel to reduce the dependence upon oil, and to desalinate water in areas where fresh water is in short supply. To deliver this benefit, new systems will be needed, requiring nearterm deployment of nuclear plants and significant research and development (R&D) on nextgeneration systems.
Figure 3. Nuclear Power Reactor Grid Connections and Shutdowns, 19562011 (Source: IAEA-PRIS, MSC, 2011) However, challenges still exist to further large-scale use of nuclear energy: (1) nuclear energy must be sustainable from the standpoint of its utilization of nuclear fuel resources as well as the management and disposal of nuclear waste, (2) the units must operate reliably and be economically competitive, (3) safety must remain of paramount importance, (4) deployment must be undertaken in a manner that will reduce the risk nuclear weapons proliferation, (5) new technologies should help meet anticipated future needs for a broader range of energy products beyond electricity, and (6) governments need to support the revitalization of their nuclear R&D infrastructures. The first four are the major goals of Generation IV; the latter two have become increasingly important in recent years. [6] 2. GIF mission The Generation IV International Forum has thirteen members (Argentina, Brazil, Canada, France, Japan, the Republic of Korea, the Republic of South Africa, the United Kingdom and the
The first generation was advanced in the 1950s and 60s in the early prototype reactors. The second generation began in the 1970s in the large commercial power plants that are still operating today. Generation III was developed more recently in the 1990s with a number of evolutionary designs that offer significant advances in safety and economics, and a number have been built, primarily in East Asia. Advances to Generation III are underway, resulting in several (so called Generation III+) near-term deployable plants that are actively under development and are being considered for deployment in several countries. New plants built between now and 2030 will likely be chosen from these plants. Beyond 2030, the prospect for innovative advances through renewed R&D has stimulated interest worldwide in a fourth generation of nuclear energy systems 63 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
United States) which are signatories of its founding document, the GIF Charter. The purpose of the GIF-Generation IV International Forum and the vision for Generation IV were defined in GIF Charter: the development of concepts for one or more Generation IV nuclear energy systems that can be licensed, constructed, and operated in a manner that will provide a competitively priced and reliable supply of energy to the country where such systems are deployed, while satisfactorily addressing nuclear safety, waste, proliferation and public perception concerns.
Figure 4. Structure of the Gen IV International Forum The Charter it was signed by Switzerland in 2002, EURATOM in 2003 and the Peoples Republic of China and the Russian Federation, both in 2006 signed the Charter. Among the signatories to the charter, ten members (Canada, EURATOM, France, Japan, and the Peoples Republic of China, the Republic of Korea, the Republic of South Africa, the Russian Federation, Switzerland and the United States) have signed or acceded to the Framework Agreement** (FA). Parties to the framework agreement formally agree to participate in the development of one or more Generation IV systems selected by GIF for further R&D. The countries have joined together to form the Generation IV International Forum (GIF) to develop future-generation nuclear energy systems that can be licensed, constructed, and operated in a manner that will provide competitively priced and reliable energy products while satisfactorily addressing nuclear safety, waste, proliferation, and public perception concerns. The objective for Generation IV nuclear energy systems is to have them available for international deployment about the year 2030, when many of the worlds currently operating nuclear power plants will be at or near the end of their operating licenses. 3. Goals for Generation IV The goals defined by GIF Roadmap, have three purposes: first, they serve as the basis for developing criteria to assess and compare the systems in the technology roadmap. Second, they are challenging and stimulate the search for innovative nuclear energy systems - both fuel cycles and reactor technologies. Third, they will serve to motivate and guide the R&D on Generation IV systems as collaborative efforts get underway.
**
http://www.gen-4.org/PDFs/GIFcharter.pdf http://www.gen-4.org/PDFs/Framework-agreement.pdf 64 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
Eight goals for Generation IV are defined in the four broad areas of sustainability, economics, safety and reliability, and proliferation resistance and physical protection. Sustainability goals focus on fuel utilization and waste management. Economics goals focus on competitive life cycle and energy production costs and financial risk. Safety and reliability goals focus on safe and reliable operation, improved accident management and minimization of consequences, investment protection, and essentially eliminating the technical need for off-site emergency response. The proliferation resistance and physical protection goal focuses on controlling and securing nuclear material and nuclear facilities. Table 1. Goals for Generation IV of nuclear energy systems Broad area Sustainability1 Goals Generation IV nuclear energy systems will provide sustainable energy generation that meets clean air objectives and promotes long-term availability of systems and effective fuel utilization for worldwide energy production. Generation IV nuclear energy systems will minimize and manage their nuclear waste and notably reduce the long-term stewardship burden, thereby improving protection for the public health and the environment. Generation IV nuclear energy systems will have a clear life-cycle cost advantage over other energy sources. Generation IV nuclear energy systems will have a level of financial risk comparable to other energy projects. Generation IV nuclear energy systems operations will excel in safety and reliability. Generation IV nuclear energy systems will have a very low likelihood and degree of reactor core damage. Generation IV nuclear energy systems will eliminate the need for offsite emergency response. Generation IV nuclear energy systems will increase the assurance that they are a very unattractive and the least desirable route for diversion or theft of weapons-usable materials, and provide increased physical protection against acts of
Sustainability2
Economics1 Economics2 Safety and Reliability1 Safety and Reliability2 Safety and Reliability3 Proliferation Resistance and Physical Protection1
Source: GIF Technology Roadmap
The Generation IV of nuclear energy systems is intended to meet the above goals (while being at least as effective as the third generation in terms of economic competitiveness, safety and reliability) in order to provide a sustainable development of nuclear energy. The goals adopted by GIF provided the basis for identifying and selecting six nuclear energy systems for further development, systems that will be described lower. 4. Innovative systems of Generation IV The goals adopted by GIF provided the basis for identifying and selecting six nuclear energy systems for further development. The motivation for the selection of six systems it was to: Identify systems that make significant advances toward the technology goals; Ensure that the important missions of electricity generation, hydrogen and process heat production, and actinide management may be adequately addressed by Generation IV systems; Provide some overlapping coverage of capabilities, because not all of the systems may ultimately be viable or attain their performance objectives and attract commercial deployment; Accommodate the range of national priorities and interests of the GIF countries.
The six Generation IV systems are summarized in the table and schematic details about each technology are presented in the figures below. Table 2. GEN IV nuclear energy systems chosen by GIF Generation IV System Gas-Cooled Fast Reactor System Lead-Cooled Fast Reactor System Molten Salt Reactor System Sodium-Cooled Fast Reactor System Supercritical-Water-Cooled Reactor System Very-High-Temperature Reactor System Acronym GFR LFR MSR SFR SCWR VHTR
Figure 5. The schematic representation of the six GENIV nuclear energy systems
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5. Romanian position and implication Romanian national strategy regarding nuclear is focus on: percentage increase (from 18% actual to 30-40%) of nuclear energy in total electricity production; continue CANDU technology (by completion of Cernavoda NPP, meaning end of U3&4); on short and long term implications in R&D of LFR technology, ending with hosting ALFRED (in February 2011 Romanian Government approved the Memorandum of Ministry of Economy for the Romanian option to host ALFRED; Memorandum was initiated by INR; INR contributed to the national debate on the issue); [8] replacing the current NPP with new technologies - on very long term (GENIV commercial systems). CONCLUSIONS A reliable and accessible supply of energy produced in a sustainable manner is fundamental for the development of modern society. The future energy mix will be determined by the availability of technologies, life cycle generating cost, environmental and health impacts, security of supply and public acceptance. Nuclear energy has an important feature: it potentially provides a stable base load quasi non-CO2 emitting source of energy that is readily available and can be deployed on a large scale to meet even fast growing energy demand. Nevertheless, the road to commercial deployment of Generation IV systems still appears to be long, having numerous technological challenges. GIF has demonstrated political willingness to support and promote the development of sustainable nuclear energy systems, as well as enthusiasm on the part of the researchers involved in the Forums collaborative R&D to surmount these challenges. Already, major achievements have been accomplished within the GIFs Project Arrangements. Besides this, the development of new generation reactors it has others benefits: the increase of the overall share of nuclear energy, building world teams, attractive research topics that can be of interest for young scientist of many disciplines. Particularly, for Romania is a great opportunity to participate in R&D of GENIV nuclear energy systems and have access to innovative technologies to support sustainable development. For this purpose, INRs R&D programmes already included some specific studies (mechanical properties of austenitic and martensitic steels, tantalum and niobium alloys, investigations on candidate materials for fuel cladding and SG tubes, corrosion in lead environment, methods for Po separation, methods for thermal& mechanical testing of materials and components, CFD methodology for LFR investigations, Design of corrosion loops, PSA for LFR, methodology for isotopic inventory calculation, DPA calculation, impact of lead on radioactive waste management, impact of ALFRED on geological disposal). BIBLIOGRAPHY [1]. M. Schneider, A. Froggatt, S. Thomas, Nuclear Power in a Post-Fukushima World 25 Years After the Chernobyl Accident, The World Nuclear Industry Status Report 20102011. [2]. IAEA NP-T-1.8, Nuclear Energy Development in the 21st Century: Global Scenarios and Regional Trends, Vienna 2010. [3]. L. Gronlund, D. Lochbaum, E. Lyman, Nuclear power in a warming world, Assessing the Risks, Addressing the Challenges, Union of Concerned Scientists, December 2007.
ALFRED Advanced Lead-Cooled Fast Reactor European Demonstrator INR Institute for Nuclear Research-Pitesti The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
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[4]. GIF, GIF R&D Outlook for Generation IV Nuclear Energy Systems, August 2009. [5]. Peter Rullhusen, Nuclear Data Needs for Generation IV Nuclear Energy Systems, Proceedings of the International Workshop, Belgium 2005. [6]. GIF-002-00, A Technology Roadmap for Generation IV Nuclear Energy Systems, December 2002. [7]. GENIV International Forum, Annual Report, 2010. [8]. S.C. Valeca, C. Paunoiu, I. Turcu, ALFRED: Current Status and Future Developments in Romania, Nuclear 2012 Conference, Pitesti, Romania, 16-18 May 2012.
V-4Cr-4Ti ALLOY-A PROMISING CORE CLADDING MATERIAL FOR GEN IV REACTORS D. Ohai
Institute for Nuclear Research, Pitesti, Romania
ABSTRACT The refractory metal-base alloy, having a very good behavior at high temperature and pressure, was studied for use in nuclear field. In Europe, the effort was focused for use of refractory metal-base alloy in fusion reactor. The use of refractory metal-base alloy in Gen IV Reactors was not studied because there are very much difficulties in fabricability of cladding, especially at tubes manufacturing. The literature study performed in INR shown possibility to use the refractory metal-base alloy, especially Vanadium-base alloys, as cladding material. The most promising material developed by USA, Japan and Russia is V-4Cr-4Ti Alloy because: The research on vanadium base alloys `covered a very large types of combinations between V and Ti, Cr [V(0-20)-Ti(0-20)] completed by addition of others elements (Si, Al, Y, etc) to improve the alloys properties and behaviour in extreme conditions and reducing impurities content The characterisation and testing condition (under and out of irradiation) was larger, also. Fabrication of small (30 kg), medium (200 kg) and larger ingots (>500 kg) of V-4Cr-4Ti by USA, Japan and Russia (in collaboration or not) contributed essential to improving the properties of this alloy and the content of impurities (O, C, N). For the characterisation and testing of V-4Cr-4Ti alloy participated USA, Japan, Russia, Germany and Spain. The thin wall tubes was obtained and the technologies are in progress
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INR EXPERIMENTAL CONTRIBUTIONS TO THE FP7- STYLE PROJECT Maria Roth, Vasile Piigoi, Maria Mihalache, Ionut Niu
ABSTRACT
This paper outlines INR experimental contributions to the Collaborative Project STYLE (Structural Integrity Assessment for Safety and Lifetime Management of the Reactor Coolant System Piping and Components-other than the Pressure Vessel) carried-out in the European Framework Programme FP7. As STYLE Project partner, INR carried-out tests on the structural material used to perform one of the Mockups. Stainless Steel 316 L material supplied by Institute de Sudure, IdS, France has been characterized from the mechanical and microstructure point of view. Further, the experimental data will be used as input in the other Working Packages. According to the test matrix agreed in the framework of the WP, tensile tests at room temperature has been done on both directions of the tub. For a better and complete characterization of the material supplementary tests and analysis have been applied, as follow: Brinnell Hardness Tests; Metallographic Analysis; SEM investigation of the fracture surfaces. The experimental investigations comply with the ASTM Standards requirements, applied for metallic materials and the Testing Procedure developed and applied at INR, in according to the Quality Program. Keywords: nuclear structural material, mechanical properties
INTRODUCTION The main objective of the STYLE Project (Structural Integrity Assessment for Safety and Lifetime Management of the Reactor Coolant System Piping and Components-other than the Pressure Vessel) carried-out in the EURATOM FP7 Programme is to assess, optimise and develop the use of advanced tools for the structural integrity assessment of reactor coolant pressure boundary components (RCPB) relevant to ageing and life time management and to integrate the knowledge created in the project into mainstream nuclear industry assessment codes. The STYLE TOOLS will include best practice guidelines based on advanced tools, on improvement and development of engineering assessment methods, EAM, considering both deterministic and probabilistic approaches. Integrity assessment case studies and large scale demonstration experiments will be performed on Mock-ups of safety-relevant components. The Project will interact with the European Network of Excellence NULIFE [1] The Institute for Nuclear Research, INR, Romania, is directly involved in the experimental, modelling and computing activities of the STYLE Project, being one of the twenty partners. To date, the results carried-out as part Material Characterization Working Package, WP 1.3, including SS 316L Tub material properties evaluation are presented. This material will be used to manufacture one of the relevant Mock-up of the Project. In the same time the experimental data will be used as input values for other WP-ies. The experimental investigations are carried-out in according with the ASTM Standards requirements, applied for metallic materials (ASTM E-8, [2], ASTM E-112, [3]) and the Testing Procedure developed and applied at INR, [4], in according to the Quality Program.
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TESTING METHODOLOGY AND RESULTS A 316L Tube offered by Institut de Soudure, France, has been used to investigate the material properties at room temperature. To perform the tensile tests a Static & Dynamic Materials Testing System 30KN, equipped with extensometer, made in Swiss by Walter+Bai, has been used, Figure 1. Longitudinal (L) and Transverse (T) samples cut from the 316L unwelded tube section (OD=250mm, thickness=27 mm), Figure 2, have be machined following the ASTM E-8M Standard, Figure 3, having the gage length, GL=25 mm and the Figure 1. Walter+Bai Universal total length of 100 mm. Testing System
Figure 1. Sample Dimensions (mm) Figure 2. Samples machining: L= longitudinal directions; T = transversedirection
Table 1 summarises the mechanical properties values for: yield stress, (YS0.2%, YS1%), ultimate tensile stress UTS, and elongation on 25 mm, 25mm. The average values and the statistical results are included in Table 2, for each direction of the tested 316L Tube. Table 1. Mechanical properties Tube Sample YS0.2% (MPa) Direction ID Cod L2 256 Longitudinal L4 241 L5 243 L6 239 T1 221 Transverse T2 231 T3 218 T5 218
YS1% (MPa) 302 283 286 281 285 280 273 270
UTS (MPa) 564 558 556 545 562 555 545 554
25mm (%) 61 60 60 61 61 59 58 58
Table 2. Statistical analysis - Mechanical Properties Tube YS0.2% YS1% Direction (MPa) (MPa) minimum 239 281 Longitudinal maximum 256 302
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UTS (MPa) 545 564
25mm (%) 60.00 61.00
Transverse
average standard dev minimum maximum average standard dev
245 7.8 218 231 222 6.3
288 9.4 270 285 277 6.6
556 7.8 545 562 554 7.6
60.40 0.42 58.00 60.80 59.10 1.24
Figure 4 outlines the difference, of about 9%, of the YS0.2%, yield stress values between the two directions of the 316 Tube, longitudinal, respectively transverse. If the plastic deformation is increased this difference is reduced, at 3% for YS1%. The ultimate tensile strength, UTS, values and total elongation are identically on both directions.
L 600 T
500
400 MPa
300
200
100
0 YS 0.2% YS 1% UTS elon Mechanical Properties
Figure 2. Mechanical Properties Comparision of 316L Tube on longitudinal (L) and transverse (T) directions
From the microstructure point of view, analyzed by the metallographic technique by using a Zeiss type optical microscope, the grains are larger in the transverse direction. The average grain size is about 42m in the longitudinal direction (Figure 5) and 49m in the transverse one (Figure 6).
Figure 5. Tube microstructure, longitudinal direction, average grain size = 42m
Figure 6. Tube microstructure, transverse direction, average grain size = 49m
The measured grain sizes values, d, are verifying the well known relation correlating this parameter with the yield stress: YS d-1/2.
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The fracture surfaces analysis of the tested samples, are in agreement with the mechanical and microstructure results. The micrographs have been obtained by a TESCAN scanning electronic microscope. The fracture occurs by dimple fracture. The transversal-radial aria presents a large grain size structure, well defined, containing depth and conical shape dimples corresponding to the high deformation level (Figures 7a and 7b). On the longitudinal-radial fracture surface the dimples are quite shallow, involving the micro voids joining by shear along the slip bands (Figures 8a and 8b).
Figure 7. Fracture surface of a sample tested under uniaxial state of stress in the longitudinal direction of the 316L Tube: a) - ( x 35), b) (x 295)
Figure 8. Fracture surface of a sample tested under uniaxial state of stress in the transverse direction of the 316L Tube: a) - ( x 35), b) (x 295) Table 3 is containing the Brinell measurements obtained by using a WOLPERT type Hardness system, made in Germany. Table3. Brinell Hardness Values Tube Sample Direction ID Cod Longitudinal L3 L8 Transverse T4 T9
2.5 HB/187.5kgf 150,149,148,149,148 148,150,150,145,148 151,148,151,150,148 150,151,148,150,148
HB Mean Value 149 148 150 149
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The analysis of the Brinell Hardness results have no suggest a significant difference of the material behaviour on the two directions of the 316L Tube, longitudinal, transverse respectively. CONCLUSIONS A detailed material properties characterization has been performed on Stainless Steel 316 L tube material used to carried out one of the experimental Mock-up of the STYLE Project. Mechanical tests and microstructure analysis have been done in according with the ASTM Standards requirements, applied for metallic materials; The experimental results shown a textured behavior of the material at low deformation. The yield stress value at 0.2% deformation is lower in the circumferential direction, about 9%, probably due to the sliding bands more favourable orientated to deformation. If the plastic deformation is increased the behavior is identically, independently of the stress direction; The mechanical properties will be used as input data for the structural integrity assessment of the experimental Mock-up manufactured from unwelded and unrepair SS 316L material. Acknowlegments The research was carried out as part of the Collaborative STYLE Project in the framework of the FP7 European Programme managed by AREVA GmbH Germany. REFERENCES [1] *** Structural Integrity Assessment for Safety and Lifetime Management of the Reactor Coolant System Piping and Components-other than the Pressure Vessel Project - STYLE - Seventh Framework Programme of EURATOM for Nuclear Research and training Activities (2007-2011), Nuclear Fission and Radiation Protection Theme, GA 249648 [2] *** ASTM E-8M - 96 Standard Test Methods for Tension Testing of Metallic Materials. [3] *** ASTM E-112 - 95 Standard Test Methods for Determining Average Grain Size [4] *** INR - Procedure Tensile Tests Procedure Mechanical Procedure under uniaxial state of stress in the RT-1000C Temperature Range
INR CONTRIBUTION TO THE FP 7 STYLE PROJECT AS CONCERNING LBB CONCEPT Vasile Radu
ABSTRACT
This paper outlines INR contributions to the Structural Integrity Assessment for Safety and Lifetime Management of the Reactor Coolant System Piping and Components-other than the Pressure Vessel Project, STYLE, carried-out in the European Framework Programme FP7. The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 73
N Nu uc ea ar Po er na an nd df us n cl le rP ow we r fi is ss si io on fu si io on f The objective of the project is to assess, optimise and develop the use of advanced tools for the structural integrity assessment of reactor coolant pressure boundary components (RCPB) relevant to ageing and life time management and to integrate the knowledge created in the project into mainstream nuclear industry assessment codes. The STYLE TOOLS will comprise best practice guidelines on the use of advanced tools, on improvement and qualification EAM as a part of European Leak-before-break (LBB) procedures and on life time management of the integrity of RCPB components in European nuclear power plants. INR Pitesti is directly involved in the experimental, modelling and computing activities of STYLE project. INR Pitesti is responsible to manage the Probabilistic assessment of LBB and LBB and Assessment Methods Work Packages, having as objectives to provide an overview of state-of-art probabilistic approaches to Engineering
Assessment Methods including Leak Before Break in various countries and to define STYLE LBB case studies associated with experiments planned to be performed on three Mock-ups during the subsequent stages of the STYLE project. From the point of view of activities already carried out or in progress in the framework of STYLE project, with good results that were appreciated by partners, one can conclude that INR is a viable strong player for the international research area, mainly focussed in the nuclear energy.
UNSATURATED HYDRAULICS AND CONTAMINANT TRANSPORT SIMPLE TEST MODEL FOR ALLIANCES AND FEHM BENCHMARK Alina Constantin1, Daniela Diaconu1, Alain Genty2
1
Institute for Nuclear Research, Romania, 2CEA Saclay, France
ABSTRACT
ALLIANCES is a software platform allowing simulation of the characteristics phenomena of all disposal and storage situations and was developed by CEA, ANDRA and EDF. It was licensed to INR in the framework of the NSRAWD project aiming to model and solve the problems related to nuclear waste disposal sites in Romania. FEHM is an American numerical simulation code for subsurface transport processes and has been used to simulate groundwater and contaminant flow and transport in deep and shallow, fractured and un-fractured porous media. INR received a license to use it and developed several models for the Saligny site, a possible location for the near future national LILW repository. The purpose of this study is to propose a simple test model in order to make a comparison of results generated by the two codes. The problem refers to unsaturated water flow and contaminant transport in a two layered soil system in transient state. The profiles obtained were similar in both water flow and contaminant transport problems. Keyworks: contaminant transport, water flow, Alliances, FEHM
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MICROSTRUCTURAL CHARACTERIZATION OF OXIDE LAYERS FORMED ON CARBON STEELS IN SECONDARY CIRCUIT CONDITIONS OF CANDU REACTORS M. Stnciulescu, A. Dinu, M. Mihalache
Institute for Nuclear Research-Piteti, Cmpului Street, No.1, Mioveni, Arges, e-mail: mada.stanciulecu@nuclear.ro
ABSTRACT
The carbon steels are widely used in the construction PHWR secondary circuits. Degradation by corrosion of carbon steels in CANDU-PHWR conditions is a real economic problem in the nuclear industry and that is why it needs frequent inspections, followed by reconditioning, or, sometimes, total exchange of components. In this context, of greate interes is the determination of the oxides that can be formed on the surface of the carbon steel components during CANDU operation. This paper presents the posibility of using X-ray Diffraction, and especially Grazing Angle Incidence X-ray Diffraction (GIXRD) to identify the oxides, also the layout of the oxides in the analysed oxide layers. The rezults are correlated with Scanning Electron Microscopy (SEM) images to have a better microstructural characterization of the oxide films. The analized material is SA106 carbon steel autoclavized in demineralizated water with AVT at a pH of 9.7 0.1, a temperature of 2655 oC and a pressure of 6.7 0,5MPa. Keywords: oxidation kinetics, GIXRD, carbon steel
1. Introduction CANDU-PHWR Reactors (CANadian Deuterium Uranium Pressurized Heavy Water Reactors) have two independent systems: one for the moderator and one for the cooling agent. The materials used for the secondary circuit have to respect some specific tasks for corrosion limitation, minimization of the radioactive isotopes production and the activity transportation in the circuit. To mitigate the corrosion process there are programs of monitoring the chemistry of the aqueous medium of the secondary circuit as a modality to upgrade the management of this circuit. An important factor in understanding the causes and the mechanisms of corrosion is the water chemistry control. The chemical control in nuclear reactor circuits consists of: the addition of chemicals to minimize the harmful effects of products generated by radiolysis; the adjustment of the pH to values that correspond to a low corrosion rate of the structural materials and that compensate the acidity variation; the minimization of chemical impurities concentration, which catalyses the degradation material, coolant and protective oxide coatings [2]. There are other factors that influence the corrosion but one of the most important is the cleaning state of the material. One of the principal materials used for the secondary circuit (cooling agent system) of PHWR reactors is carbon steels. Carbon steels are ductile, relatively easy to weld and inspect. Degradation by corrosion of carbon steel compounds represents an expensive problem in the nuclear industry and that is why it needs frequent inspections, followed by reconditioning or even total exchange of the compounds. Characterization of oxide films formed on metals and alloys is an important subject of study because chemical and physical properties of the oxide films can alter the mechanism and kinetics of corrosion processes. Particularly, the characterization of oxide films formed on carbon steel as nuclear material is a subject of investigation to understand environment-related material failure problems [1]. It is known that carbon steels corrosion in the aqueous medium at high temperature determines the formation of a duplex oxide layers on the material surface. The inner layer is a fine-grain compact oxide, which grows in the direction of the base material, occupying the
volume of the corroded material. The corroded iron cannot precipitate as long as the Fe2+ ions diffuse through the inner layer to the interface oxide layer/ cooling agent. If the cooling agent is already saturated in dissolved iron, Fe2+ ions resulted from the corrosion process supersaturates the existing layer at the fluid limit, determining the precipitation of de outer oxide layer [3]. In this paper, the oxide layers formed on SA106 carbon steel during exposure in secondary circuit conditions are characterized by DRX, GIXRD, metallographic microscopy and SEM. 2. EXPERIMENTAL The material investigated was carbon steel SA106, which was prepared before autoclavization conform usual metalographic proceed for sample preparation. In table 1 presents the chemical composition of carbon steel SA 106. Table 1. Chemical composition of the carbon steel used in the work Elemente (%gr) C 0.28 Ni 0.026 Mn 0.78 Cr traces Co 0.003 S 0.022 P 0.024 Si Fe
0.23 balance
The samples are paralelipipedic with the dimensions 50x15x3mm with a hole of 2.5mm at both ends. These samples were polyshed on abrasive papier untill 800 granulation, then on alumina to obtain a mirror surface. The SA106 carbon steel samples have been autoclavized in clasical AVT (All Volatile Treatment) solution containing morpholine and cyclohexylamine dissolved in demineralized water, this will be named AVT solution. The role of the amine dissolved in the demineralized water together with cyclohexylamine was to assure a final pH of 9,7; in addition a quantity of hydrazine hydrate was added to assure an oxygen concentration of 10ppb, as seen in the reactions (1) and (2)[3]: N2H4 + O2 N2 + 2 H2O N2H4 + 6 Fe2O3 4 Fe3O4 + N2 + H2O (1) (2)
The autoclavization was done in CANDU secondary circuit conditions, i.e temperature (2655oC) , pressure (6.7 0,5)MPa and pH (9,70.1). The samples were autoclaved between 20 and 70 days. The testing system consisted of a steady state Prolabo autoclave with 1L capacity. This method consists in the exposure of the metallic samples in different aqueous environments, at elevated temperatures and pressures, as close as possible of the conditions present in the secondary circuit of CANDU systems. The oxidized samples were microstructurally characterized by DRX, GIXRD and SEM. The compositions and layout of the oxide layers have been determined using an X-ray diffractometer. The aquisitionation of the diffractograms were made with the XPert PRO MPD Diffractometer existent in LADICON laboratory at SCN Pitesti . It is very difficult to analyze thin films due to their small diffracting volumes, resulting in low diffracted intensities compared to those of the substrate and background. By increasing the path length of the incident beam through the film, the film intensity is increased. By GIXRD it is possible to perform many of the XRD analyses with the added ability to have supplementary information as a function of depth by collecting successive diffraction patterns with varying the incidence angles. The incidence angle is fixed and very small (<5), increasing the path length of de incident beam through the film and the detector is rotated with a 2 angle. The layout of the oxide layers present on the sample surface can be determined by varying the incidence angle [4].
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The microstructural characterization of the oxide layers was made using a VEGA II LNU microscope with the secondary electron detector. The microscope NEOPHOT 2 was used to determine the thickness and homogeneity of the oxide films. 3. RESULTS AND DISCUSSIONS As previously said, the phase composition of the oxide layers formed on the carbon steels samples were assessed using X-ray diffraction. The first step is the qualitative and semi-quantitative analyze of the samples by DRX in normal geometry. The layout of the oxide layers in the total oxide layer is determined by GIXRD methode.
Figure 1. Spectrum of the samples autoclavized 20 days in AVT solution Fig.1 presents the diffractogram of samples autoclavized 20 days in the already specified solution. It can be seen that the principal oxides formed are hematite and magnetite. The diffraction lines for iron are very high meaning that the oxide layer is very thin. The semi-quantitative analyse gives a concentation of 40% Fe, 38% Fe2O3-hematite and 22% Fe3O4-magnetite in the analysed layer. To have a better ideea of the oxide film composition and layout it is necessary to use the grazing angle X-ray diffraction method. By GIXRD the evolution of the oxide layers in function of the incidence angle can be determined. The incidence angles used for the comparation of the diffractograms are 2 and 0.5. Comparing the diffractograms (Fig. 2) aqusitioned at small incident angles, it can be seen that at 2 high diffraction lines of iron apare again, so it is confirmed that the oxid layer is thin.
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Figure 2. Comparation between the diffractograms aquisitioned at different angles (theta-theta,2,0,5) for the sample autoclaved 20 days in degazated AVT solution At an incident angle of 0.5, the intensity report between the diffraction lines hematite/magnetite is higher then that obtain in theta-theta configuration and at 2, indicating that the Fe2O3 layer is on the top of the oxide film and magnetite is at the interface oxide film/metal (substrate).
Figure 3. Difractograma of the samples autoclaved 70 days in AVT solution After 70 days of autoclavization the oxide film gets thicker. The oxide film composition is the same, magnetite and hematite. The iron specific diffraction lines descrease and those of the oxides increase even in - configuration, showing that the oxide film is thicker than the one formed after 20 days in the aquous solution (Fig. 3). Also, the semi-quantitative analyse shows a decrease in the Fe concentration (20%) and an increse in the oxide concentration (hematite 41% and magnetite 39%) in the analysed layer. Fig. 4 reprezents the comparation between the diffractograms aquisitioned at different incident angles for the samples autoclavisated 70 days in the same solution. It can be seen that the lines of iron disapear at 2 incidence, an confirmation that the oxide film is thicker than in the first case. Also, the diffraction lines of hematite increase with the decrease of incidence angle and those
of magnetite decrease, rezulting that the outer layer is formed of hematite and the inner layer of magnetite.
Figure 4. Comparation between the spectra aquisitioned at different angles (theta-theta, 2, 0,5) for the sample autoclavizated 70 days in AVT solution The SEM pictures of the oxide film formed after 20 days of exposure are shown in Fig.5. Scanning at lower magnifications demonstrated that the oxide film is not homogenously covering all the surface of the sample. The film formed on the sample autoclavised 70 days in the same solution is homogenous on the surface of the carbon steel (Fig.6).
Figure 5. SEM imagies on the film formed on Figure 6. SEM imagies on the film formed on carbon steel autoclavizated 20 days in AVT carbon steel autoclavizated 70 days in AVT solution solution It is metallographically confirmed that after 20 days of autoclavization a thin, non-uniform oxide film forms and after 70 days a thinker and much uniform oxide film forms on the surface of the carbon steel samples (Fig.7). Figure 7. Metallographies of films formed on carbon steel autoclavized in AVT solution: (a) after 20 days and (b) after 70 days
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The results of SEM are in concordance with those obtained by X-ray diffraction. The micrography in Fig.8 shows a duplex layer morphology, composed of small dimenstion rombohedric crystals in the inner part of the oxide film. This inner layer is a tightly adherent, finegrained compact layer of magnetite Fe3O4, which has the role to protect the material from corrosion and is well formed after a bigger number of days in the corrosive environment. The outer layer is a loosely adherent, different sizes particule layer of hematite-Fe2O3. This layer does not protect the material from corrosion and it can be spalled and carred out in all the circuit and can form the crud.
Figure 8. SEM imagies on the film formed on carbon steel autoclavizated 70 days in AVT solution On the bases of the owned experimental results and those presented in the literature, it can be concluded that the evolution of the oxide layer formed on carbon steel components is a dynamic process that implies both the deposition mechanism and the releasing of the superficial compounds mainly by erosion and dissolution. 4.CONCLUSIONS The oxide films formed on carbon steel SA106 in secondary circuit conditions demineralized water with amines at temperature (2655oC) , pressure (6.7 0,5)MPa and pH (9,70.1) were analysed by DRX, GIXRD, SEM and metallography. The DRX and GIXRD analyse technigues shown that the thicker oxide film was found on the specimens autoclavized 70 days and that the oxide films are formed of a duplex oxide layers on the material surface. The principal oxides formed are magnetite and hematite. By GIXRD analyses it can be said that the magnetite layer is found at the interface substrate/oxide film and the hematite represents the outer layer of the oxide film. The SEM examinations confirmed that the inner layer is a tightly adherent, fine-grained compact layer of magnetite Fe3O4 and the outer layer is a loosely adherent, different sizes particule layer of hematite-Fe2O3. Metallography conforms the results of X-ray diffraction and SEM. GIXRD is a fiable technique for the determination of the oxide layers layout in the total oxide films. Acknowledgements The authors acknowledge the assistace of M. Radulescu and thank her for the valuable discussions.
REFERENCES [1] Kim Y.-J, Analyses of oxide film formed on type 304 stainless steel in 288C water in containing oxygen, hydrogen, and hydrogen, Corrosion-Vol. 55, No.1, 1999, pp.81-88; [2] Radulescu M. et al., Management of CANDU 6 secondary circuit water chemistry using several amines, JNRD, No.1, 2012,pp.13-18; [3] Radulescu M, R.I.7883/2007, Diminuarea acumularii produsilor de coroziune pe componentele din otel carbon prin reglarea pH-ului in circuitul secundar, 2007; [4] Stanciulescu M, Dinu A, X-ray diffraction- a complex method for material characterization, Coferinta ICSI 2011.
THE WHY WHAT AND HOW IN NUCLEAR KNOWLEDGE MANAGEMENT Cristian Voiculescu1, Eleonora Andreea Dragan2
Institute for Nuclear Research Pitesti, Campului Street, 1, Mioveni, 115400, Romania, Web: http://www.nuclear.ro, Phone: +40 248 213 400, Fax: +40 248 262 449; 1 Metrology & Information Technology Laboratory, Institute for Nuclear Research Pitesti Phone: +40 248 213 400, Extension: 412, E-mail: cristian.voiculescu@nuclear.ro 2 Foreign Relations, Technology Transfer and Administration, Institute for Nuclear Research Pitesti Phone: +40 248 213 400, Extension: 395, E-mail: eleonora.dragan@nuclear.ro
ABSTRACT
Over the recent years, an increased interest has been noticed concerning knowledge management in nuclear organizations. The Nuclear field is a highly regulated and knowledge based industry, thus its ongoing development depends heavily on the employees expertise. Long term nuclear energy scenarios show an industry whose major challenges are ageing workforce, declining student enrolment numbers and the risk of losing accumulated knowledge and experience. Given this already present issues, a knowledge management program in a nuclear organization seems to become a necessity. The paper aims to summarize the reasons that led to the development of Nuclear Knowledge Management Programs, a brief insight over the main steps in developing a NKM program from researching and design to implementation. A special attention will be given to the NKM Tools and Methodologies utilized in capturing and transforming different types of knowledge. The paper will highlight the current state of Nuclear Knowledge Management and the organizations involved in researching and developing this field. Also, the paper will present the Romanias position concerning the NKM necessity, the approach used to implement a NKM program, its current state of development and future projects. Keywords: Nuclear Knowledge Management, NKM Tools
INTRODUCTION To understand the knowledge management concept, first there has to be made a distinction between data, information, and knowledge. Generally speaking, data are raw facts. For data to be of value, it must be processed to obtain information, based on which decisions can be made. Knowledge is perceived as meaningful information. Knowledge is derived from information. It
results from making comparisons, identifying consequences, and making connections. Some experts include wisdom and insight in their definition of knowledge. Wisdom is the utilization of accumulated knowledge. So, knowledge is neither data nor information. Knowledge is an understanding, and one gains knowledge through experience, reasoning, intuition and learning. Individuals expand their knowledge when others share their knowledge, and ones knowledge is combined with the knowledge of others to create new knowledge. Good knowledge management is about getting the right knowledge, in the right place, at the right time. The right knowledge is the knowledge you need in order to be able to undertake a certain task, manage a project, make a decision or plan strategically, interpreting a piece of research or deal with suppliers and many others of the kind. The right knowledge can be obtained from a variety of sources such as research reports, journal articles, manuals, technical reports, databases and web documents, databases and more often in peoples heads. The right place refers to the point of action or decision such as in a meeting, help desk, hospital bedside and customers complaint counters. The right time is when the person or team of workers needs the knowledge. 1. KM CONCEPT Knowledge management is a multi-disciplinary field that draws from theories in economics, sociology, philosophy and psychology. Applied disciplines such as information technology, library science and business also contribute to understanding this field. KM combines and applies multiple theories to practical problems within organizations. It has a pragmatic approach that is concerned with real solutions and the ability to analyze and measure its applications accurately. Knowledge Management defines as an integrated, systematic approach to identifying, acquiring, transforming, developing, disseminating, using, sharing and preserving knowledge, relevant to achieving specified objectives [1] Knowledge management revolves around the combination of people, processes and technology, operating within culture that ideally recognizes the worth of knowledge. Knowledge management focuses on:
Figure 1. Three main components of Knowledge Management people and organizational culture to stimulate and nurture the sharing and use of knowledge; processes to find, create, capture and share knowledge; technology to store and make knowledge accessible which will allow people to work together without being located together. Above all this, people prove to be the most important component of all, given the fact that they are the ones managing knowledge and its up to them to use, reuse, and share knowledge with others. Categories of knowledge Knowledge can be categorized as explicit and tacit. Explicit knowledge is contained in documents, drawings, calculations, designs, databases, procedures and manuals. It contains all technical information gathered while carrying out R&D activities. Explicit knowledge implies declared knowledge. Explicit knowledge is why it is not a problem for the employee to tell about
rules and obviously learned facts. Very often this knowledge is already written down in books. Examples that contain explicit knowledge include NPP documentation and databases such as a website, an operational manual, records or a report of research findings. Tacit knowledge has been called what we know but dont know we know. It is the most difficult type of knowledge to recall and, thus, to transfer. Tacit knowledge includes knowledge about topics such as how to ride a bicycle or how to talk. These examples describe knowledge everybody just has. However, every individual possesses a lot of tacit knowledge.
Figure 2. The iceberg metaphor describes the relationship between Explicit & Tacit Knowledge Employees, for example, tacitly know how they persuade other people, how to behave in different situations, or how to organize a meeting. Such knowledge cannot be completely explained, since it is wholly embodied in the individual, rooted in practice and experience, expressed through skillful execution, and transmitted by apprenticeship and training through watching and doing forms of learning. [2] Experts in the area of knowledge management present explicit-tacit knowledge in the form of knowledge iceberg which demonstrate that codified (or explicit) knowledge is normally about 5% of total knowledge and 95% is implicit and tacit knowledge. The challenging barrier for knowledge organizations is that of creating a culture in which knowledge and knowledge sharing are valued and encouraged. R&D organizations generate knowledge mainly from within the organization. Another aspect is the tapping of tacit knowledge. The knowledge that resides in the experts mind has to be recorded so that when an expert leaves the organization, his knowledge will still be available for the benefit of organization. The issues to be addressed are: Appreciation of importance of knowledge captured; Knowledge loss while capturing; Mechanisms for transferring and transforming knowledge. So, why is knowledge management useful? It is useful because it places a focus on knowledge as an actual asset, rather than as something intangible. In so doing, it enables the organization to better protect and exploit what it knows, and to improve and focus its knowledge development efforts to match its needs. In other words: It helps firms learn from past mistakes and successes. It better exploits existing knowledge assets by re-deploying them in areas where the firm stands to gain something, e.g. using knowledge from one department to improve or create a product in another department, modifying knowledge from a past process to create a new solution, etc. It promotes a long term focus on developing the right competencies and skills and removing obsolete knowledge. It enhances the firm's ability to innovate. It enhances the firm's ability to protect its key knowledge and competencies from being lost or copied.
Unfortunately, KM is an area in which companies are often reluctant to invest because it can be expensive to implement properly, and it is extremely difficult to determine a specific ROI. Moreover KM is a concept the definition of which is not universally accepted, and for example within IT one often sees a much shallower, information-oriented approach. 2. KM IN NUCLEAR When it comes to Nuclear Knowledge Management there are several factors to take in consideration: Complexity nuclear knowledge is highly complex on both the micro and macro scale. The physical, chemical, radiological and biological interactions of materials as well as the sociological, economic, political and security aspects must all be considered as a whole. Cost due to its complexity, the creation of nuclear knowledge is quite costly. The construction of the nuclear facility and its operation are large tasks and complex engineering projects require sophisticated safety systems and specialist staff. Timescale the time period between the creation of knowledge and its use can be very long. For example, the time between radioactive waste being created and its disposal could be many decades. During this time, the information, the capability to access, interpret and understand it, must be maintained. Cooperation many individuals, organizations and Member States have legitimate cause for both contributing to and accessing the nuclear knowledge base. The information and data used and the experiences, skills and insights applied must be carefully monitored to guarantee robustness. Education is essential for people to acquire the experience and insights needed to create new knowledge and apply it to emerging challenges. 2.1. KM Tools and Techniques The purpose of this section is to provide a brief outline of the KM tools and techniques that nuclear R&D organizations should consider to help deliver business benefit to the organization. 2.1.1. KM analysis tools KM maturity self-assessment this tool is used to help determine the current KM capability in an organization and to assist in identifying KM areas for future improvement. The IAEA has produced a self-assessment questionnaire and Excel spreadsheet specifically for nuclear R&D organizations that can be used to facilitate the process. Knowledge loss risk assessment is used to determine the potential business impact of the loss of critical knowledge from an organization Identification of critical knowledge Identification of critical knowledge is carried out to help identify those individuals who are critical to its on-going success. Rapid evidence review a rapid evidence review (RER) provides R&D organizations with a way of quickly reviewing research and development evidence on a particular subject and consolidating knowledge at the beginning of a new project or study. 2.1.2. Knowledge capture techniques The techniques used to extract tacit knowledge are of key significance to R&D organizations because there are many experts who have tacit knowledge and this is usually the most important resource of the organization and a resource that it very difficult to measure.
A performance measure used to evaluate the efficiency of an investment or to compare the efficiency of a number of different investments. To calculate ROI, the benefit (return) of an investment is divided by the cost of the investment; the result is expressed as a percentage or a ratio.
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Interview techniques interviews are important in helping to understand and capture knowledge associated with an experts role. There are three main types of interview techniques: o Unstructured interviews have an outline agenda but no pre-defined questions or structure; o Semi-structured interviews (the most commonly used) have a structured agenda with the flexibility to ask additional questions following an answer; o Structured interviews; these allow no flexibility; all questions are pre-established. Laddering and concept mapping laddering and concept mapping are diagrammatic ways of representing knowledge in a particular area or knowledge domain. Laddering uses a hierarchical approach to show relationships between concepts. A concept map is similar to a ladder. However, the layout usually starts from a central theme and shows concepts as nodes and the relationships between them as labelled arrows. Process mapping processes are characterized by stages, actions or events, with each stage having inputs and outputs. Process knowledge is often found in narrative procedures. Observation observational techniques are another valuable means of capturing tacit knowledge. These techniques are particularly useful when trying to capture special skills (e.g. calibration techniques, equipment set-up and operation, specialist welding etc.). Simply observing and making notes as the expert performs their daily activities can be useful, although this is a timeconsuming process. Constrained tasks the constrained task approach limits the choices an expert is given when capturing knowledge (e.g. structured interviews, self-assessment questionaires, quizzes and guessing games) Concept sorting sorting techniques are a well-known method for capturing the way experts compare and order concepts. This can lead to the understanding of the knowledge about properties, tasks and relationships between concepts.
Figure 3. Example concept ladder or tree.
Figure 4. Example of concept map.
2.1.3. Social interaction and knowledge sharing techniques Communities of practice community of practice (CoP) is a network of people who work on similar processes or in similar disciplines, and who come together to develop and share their knowledge in that field for the benefit of both themselves and their organization. Peer assist peer assist is a process in which an individual or team arranges a meeting or a workshop in order to make use of the knowledge and experience of other individuals or teams before embarking on a project or activity. Knowledge marketplace a knowledge marketplace can be regarded as a dating service to assist in knowledge and competence transfer. The process begins by identifying what people currently know and what they would like to know on a particular topic and then connects them as appropriate. The knowledge marketplace process can be facilitated face-to-face, on-line or via email.
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After action review after action review (AAR) is a process used to capture and evaluate lessons learned. It takes the form of a quick and informal review and discussion at the end of a project or at a key stage within a project or other activity. Knowledge caf a knowledge caf brings people together to have an open, creative discussion on topics of mutual interest. It can be organized in a meeting or workshop format, but the emphasis should be on flowing dialogue that allows people to share ideas and learn from each other. 2.1.4. IT Tools Document and content management systems document and content management systems have been used for many years to hold explicit knowledge in the form of documentation. Such systems are particularly important in R&D organizations to help maintain in electronic format items such as research papers, results of experiments, design information, component data, drawings and other data and information relating to the research center and its operations. Most systems incorporate a workflow module that allows the circulation of documentation amongst users maintaining configuration control for document updates following check and approve cycles. Examples of the most frequently deployed systems include: o Documentum (www.documentum.com); o Hummingbird (www.hummingbird.com); o Microsoft SharePoint (www.microsoft.com); o FileNet (www.ibm.com); o Livelink (www.opentext.com). Explicit knowledge search/retrieval all types of nuclear R&D organizations require personnel to be able to search for and have access to explicit knowledge. A simple search engine is often included in the document/content management systems. Knowledge base systems a knowledge-based system is a computer system that is programmed to imitate human problem solving by means of artificial intelligence and reference to a database of knowledge on a particular subject. The purpose of a knowledge base system is to: o Allow knowledge to be stored and structured; o Interface with other IT systems that contain knowledge; o Allow users to find and access knowledge; o Carry out decision making and problem solving activities to replicate human thought processes. Portals - A portal is a comprehensive access structure to resources (web super site) that provides a single, often personalized interface point for accessing and consolidating information from disparate sources. The purpose of a portal is: o An integration tool to provide easy, unified and integrated access to an organizations own resources; o An access tool for other (internal and external) information resources; o A communication tool to enable individuals, teams and communities of practice to share and discuss ideas and knowledge. In and R&D organization a portal offers many advantages: o Increases staff productivity (by reducing the time taken to access information and provide it in a more useful form.); o Providing management with powerful data management tools (for an effective overview of performance and activities); o More effective decision-making (based on access to needed knowledge); o Recognition of the value of knowledge (as a key element of human capital with significant commercial value). Collaboration and social networking tools enterprise social software, also known as Enterprise 2.0, is a term describing social software used in an enterprise (business) context.
Examples of social software include Facebook, Myspace, Flickr, Wikipedia etc. and these systems are generally used by individuals outside the work environment.
Skills/competency management systems for nuclear R&D organizations, demonstrating staff competence to regulators and clients in a very important management practice. A related activity is the actual process of maintaining and enhancing competence throughout the entire organization. IT tools are available to help do this. [3] 3. THE IAEA APPROACH IN MANAGING NUCLEAR KNOWLEDGE IAEA is engaged in leading activities towards preservation and enhancement of nuclear knowledge by complementing and as appropriate supplementing, activities by governments, industry, academia and international organizations. The Agency, in particular, should use its potential in assisting Member States to ensure the preservation of viable nuclear education and training which is a necessary prerequisite for succession planning. The mission of the Agencys NKM programme is to assist Member States to sustain and further enhance nuclear knowledge by applying modern knowledge management tools and practices. The objective is that Member States develop the capacity and means to manage nuclear knowledge as a resource for the efficient and safe implementation of both current nuclear programmes and socio-economic development in the future. Key activity areas: Providing guidance for policy formulation and implementation of nuclear knowledge management; Strengthening the contribution of nuclear knowledge in solving development problems, Facilitating knowledge creation and utilization; Implementing effective knowledge management systems; Preserving and maintaining nuclear knowledge; Securing sustainable human resources for the nuclear sector; and Enhancing nuclear education and training. 4. ASPECTS REGARDING THE ROMANIAS POSITION IN NKM The challenges and trends in the nuclear field in the recent years have convinced researchers as well as the management people that NKM is an increasingly important element that needs to be dealt with. Romania is one of the countries with a dynamic nuclear program having a research institute INR with 41 years of activity and 2 operating NPP units with another 2 in plan and looking for financing, as well as various non-nuclear applications and radioactive waste repositories. Among the key challenges of the nuclear field in Romania one can mention without any doubt the retiring staff and attracting the young generation to a career in this field. The graphs
below illustrate the aging trend of the personnel at INR and at Cernavoda NPP. The average age of the personnel has increased continuously in the last 10 years and in 2010 the research staff had an average age of 45-65 years old at INR, while at Cernavoda NPP most of the employees were ages 40-50 years old. [4]
Figure 5. Age distribution at Cernavoda NPP and INR Pitesti Another important issue that needs to be addressed is the scientific and technical heritage of several decades of nuclear development that exists in a decentralized manner in Romania as well as many Member States. This means that the tacit and explicit knowledge needs to be identified, assessed and afterwards the valuable knowledge to be preserved for future use. Also, it is important to improve the access to nuclear knowledge as sharing and pooling knowledge can contribute to the ongoing development and innovation. Nevertheless, networking education and training and working on mutually accepted curricula can make studying nuclear subjects more attractive, facilitate exchange of human resources and contribute to the development of educational quality benchmarks. In the last years, in INR were developed or some very important activities, related with the finding and implementation of the appropriate methods and tools for transfer and preservation of the relevant accumulated knowledge. Therefore, INR was involved in some activities, which were decisive for the future evolutions of its organizational knowledge management. We have to mention here the IAEA Coordinated Research Program (CRP) developed between 2006 2009 on "Comparative Analysis of Methods and Tools for Nuclear Knowledge Preservation and another Regional Contract IAEA on Strengthening Capabilities for Nuclear Knowledge Preservation started in 2007. Additionally, it is worth mentioning the involvement of INR in the setup of the Educational Network for Nuclear Physics and Engineering, REFIN, since 2005. [5] Another important initiative at the level of the regulatory body this time was a project that completed in April 2011 - Capacity Building and Knowledge Management that was funded through a grant from Innovation Norway through the Extra budgetary Programme for Safe Nuclear Energy in Romania and was carried out by the National Commission for Nuclear Activities Control (CNCAN). The programme consisted in an integrated series of projects aimed to further enhance nuclear safety in Romania and IAEA acted as the programme implementation agent. The steps in the project and the results obtained can be used as guidelines for future similar initiatives that need to be developed in the other nuclear organizations in Romania. [6] This means that a KM health check is the first step before considering any further project action. Then the KM processes map and of the KM processes overview are vital to be developed. Once the KM system is developed for a specific organization it can be implemented. To support all these actions it is required a training utilizing the Systematic Training Needs Analysis (STNA) tool, based on the IAEA Safety Standards and only in the end it should be carried out an implementation plan for ensuring sustainable education and training in nuclear safety and links with other national centers of knowledge.
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CONCLUSIONS Lately, businesses throughout the world including those enterprises engaged in activities related to or employing nuclear technology have recognized that deliberate and effective attention must be paid to the management of an organizations knowledge. As intellectual capital has come to be recognized as a principal asset, the capture, retention and utilization of an organizations knowledge has become a critical element of the business strategy formulation process. In the last twenty years, much has been learned about ways by which KM can most effectively be implemented in an organization. BIBLIOGRAPHY [1] IAEA-Tecdoc-1510, Knowledge management for nuclear industry operating organizations, IAEA, VIENNA, 2006; [2] IAEA-TECDOC-1586, Planning And Execution of Knowledge Management Assist Missions for Nuclear Organizations IAEA, VIENNA, 2008; [3] IAEA-TECDOC-1675, Knowledge Management for Nuclear Research and Development Organizations IAEA, VIENNA, 2012; [4] http://www.cne.ro/m.aspx?id=87&it=3, Annual Report INR Pitesti 2010; [5] S. Valeca, V. Balaceanu, M. Constantin, M. Valeca The Institute for Nuclear Research Pitesti Strategy On Nuclear Knowledge Preservation, Nuclear 2011; [6] http://www-ns.iaea.org/projects/roman_bulgar/romania.asp?s=8&l=62.
INVESTIGATION OF THE OXIDES FORMED ON 304L ODS STEEL AND 304L SS IN SUPERCRITICAL WATER ENVIRONMENT Maria Mihalache1, Manuela Fulger1, Constantin Paunoiu1, Mihail Mihalache2
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Institute for Nuclear Research, Pitesti, Romania Power Engineering Faculty, University Politehnica Bucharest
ABSTRACT
In order to fulfil new superior cladding the requirements for new reactor generation GIV, the austenitic 304L stainless steel was improved by oxide dispersion strengthening (ODS), using two nano-oxides: titanium and yttrium oxides. The new material resulted 304 ODS was characterised by different techniques and the behaviour in supercritical water (SCW) environment was considered. The corrosion tests have been performed in supercritical water at a temperature of about 823 K and 25 MPa pressure. The weight gains of ODS samples were measured and compared with those of the 304 L stainless steel. The weight gains of ODS samples are higher than that of the austenitic steel after 1320 hours. The oxides developed on the ODS samples in SCW are layered, thicker and more uniform oxides were observed in ODS steel after corrosion than in 304L SS. The morphology of oxide surface was investigated with backscattered electrons in a scanning electron microscope (SEM). The composition of sub-layers has been analysed using an energy dispersion X-Ray spectrometer (EDS) coupled at SEM.
Keywords: ODS steel, SCPW, cladding material

1. INTRODUCTION Development of new materials for structural applications in advanced generation IV reactors, main for fuel cladding materials, is historically a long process. The first step is the testing and characterisation of normal materials used in generation III and earlier in new reactors operating conditions, such as supercritical pressurized water (SCW) reactors. The next step in materials research and development is the introducing of other alloying chemical elements for improving the mechanical, welding properties, the irradiation behaviour and to provide coolant compatibility. For all materials it is need to perform an advanced qualification with the goal of the evaluation of the behaviour in high temperature and high dose conditions, extended operation period, coolant compatibility, and the qualification for safety assessment. Oxide dispersion Strengthened (ODS) stainless steel are considered candidate material for fuel cladding in both reactor concepts, for fission and fusion. The compatibility with cooling agent from SCW reactor, which operates at 550C, is one important issue of reactor material science. The microstructural changes of ODS steels is the adding of nono-oxides (yttrium and titanium oxides). Compared with ferritic-martensitic steels, austenitic steels are known to have superior hightemperature strength, are weld able, but have an inferior irradiation resistance [1]. The oxide dispersion strengthening of austenitic steels may improve the irradiation resistance and thus if the corrosion resistance is reliable, an attractive candidate material for cladding tubes of Gen-IV reactors will result. Subsequently, for using in SCWR the corrosion of austenitic ODS Steels in SCW must be studied. 2. EXPERIMENTAL 2.1 Materials The austenitic steels tested were A/SA - 240 type 304 L and the same steel with addition of yttrium and titanium oxides. The chemical composition of the tested alloys are presented in Table 1. Table 1. Chemical composition samples Element Percentage by Weight Maximum Unless Range is Specified 304L (ASTM A240) 304 ODS (producer) Rest 73.95 18.00-20.00 16.7 8.00-10.00 7.8 0.75 0.2 0.10 0.5 2.00 0.08 0.045 0.030 0.35 0.5
Iron Chromium Nickel Silicon Nitrogen Manganese Carbon Phosphorus Sulfur Y2O3 TiO2
The manufacturing processes of 304 ODS samples, specified by supplier, are follows: AISI 304L stainless steel powders were mechanically alloyed (MA) with 0.35% Y2O3 and 0.5% TiO2. Powders were consolidated by hot isostatic pressing process (HIP) in two steps: first step was performed for 2 hour at 1100C under a pressure of 100MPa and the second for 1 hour at 1150C under same pressure. The next fabrication process was forging of the hot isostatic pressed billet at an initial temperature of 1150-1170C, final forging temperature 970oC, forging ratio 3:1.
The forged pressed billet was hot-rolled at 1150C from a plate with a thickness of 20 mm into a plate with a thickness of 11 mm and then subjected to a subsequent heat treatment (annealing) at 1150C for 30 minutes followed by a free cooling in furnace. The samples were cut from billet by electrical discharging. An image of sample surface after electrical discharging, obtained by Scanning Electron Microscopy is presented in Figure 1.
a) b) Figure 1. SEM Images of ODS sample surface after electrical discharging, magnify a) x100, b) x2000 2.2 SCW experiments Experiments were carried out in an one liter supercritical static autoclave (Figure 2). The corrosion experiments have been performed in demineralised water at supercritical temperatures, 550oC, and a pressure of 25 MPa. The pH of solution at room temperature was about 6, and the conductivity was 0.4 S/cm2. The physical properties of SCW are different from the properties of liquid or gas, the density of SCW varies from 0.1 to 0.8 g/cm3 while the water density is 1g/cm3 and the gas density is 0.001 g/cm3 [2]. The AISI 304L SS sheet and 304-ODS block were cut in coupons of 15 x 10 x 2 mm in sizes. Prior to being exposed in autoclaves, the as received samples were polished with abrasive papers up to 1200 grade and cleaning in a mixture 1/3 acetone, 1/3 isopropyl alcohol and 1/3 benzene. During exposure in SCW environment, the oxygen concentration couldnt been controlled, only at 1000C a thermal degassing for oxygen removing has been performed. After periods of 240, 480 and 816 hours, the corrosion rate was evaluated by the weight gain/unit surface area, using a balance with readability of 1g. 3. RESULTS AND DISCUSSION 3.1 Microstructural analysis The microstructure of austenitic 304L SS was examined in polarised light after metallographic preparation. Few images of grains from austenitic 304L stainless steel after microstructural electrolytic etching with oxalic acid, 6V, 2 min are displayed in Figures 3 and 4. The optical microstructures on the longitudinal planes of the as received 304L samples depict twinned grains.
Figure 2. Supercritical Static Autoclave

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Due to the cold working of heat-treated austenitic ODS steels, the grain morphology of samples appears to be extremely elongated and parallel to the rolling direction; these characteristics usually cause the tensile anisotropy of the ODS steels. The metallographic images (figures 5 and 6) of ODS steel present oxide particles non uniform distributed in the matrix, displayed as areas with very many points combined with areas of large textured grains.
Figure 3. Metallographic image of 304 L SS sample microstructure (polarised light)
Figure 4. Metallographic image of 304 L SS sample microstructure (polarised light)
Figure 5. Metallographic image of 304 ODS Figure 6. Metallographic image of ODS sample microstructure (polarised light) sample microstructure 3.2 XPS analysis The XPS investigation has been performed by ESCALAB 250 electron spectrometer using a monochromatic Al K (1486.6eV) excitation X-ray source, with a special resolution of 500 m. For the adsorbed species removal, the analysed regions washed by Argon ions. Electrons spectrum has been acquired and processed by Thermo Avantage v4.60 software, using NIST and Handbooks of Monochromatic XPS Spectra 2005 spectrum databases. X-ray Photoelectron Spectroscopy (XPS) is a method that provide the information related to chemical composition on a surface from the photoelectron spectrum obtained by irradiation with XRays. The first, a XPS spectrum is a Counts/Binding Energy diagram that map out the emitted photoelectrons number in function of their binding energy on atomic energy levels, corresponding to each chemical element on the surface. In figure 7 is presented XPS wide-scan survey spectrum obtained for a 304 ODS coupon exposed in supercritical water at 550oC for 44 days. In spectrum were presented peaks of the chemical elements identified on the investigation surface, and its composition on surface are presented in the table 2.
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Figure 7. Wide-scan survey spectrum for 304 ODS sample, after 44 days of exposure in SCW at 550oC For each element identified, the peaks were deconvoluted. After processing were identified tree peaks corresponding to follows iron oxides: FeO and gama-Fe2O3, and two peak for chromium corresponding to metallic chromium, and to chromium oxide Cr2O3. In figure 8 is presented XPS wide-scan survey spectrum obtained for a 304 ODS coupon exposed in supercritical water at 550oC for 56 days. In spectrum were presented peaks of the chemical elements identified on the investigation surface, and the its composition on surface are presented in the table 3. Table 2. Chemical composition of oxides on the surface of 304 ODS sample 44 days SCW 550oC Energy level Fe2p3 Cr2p3 O1s C1s Mo3d5 Binding Energy [eV] 710.73 574.06 531.31 285.99 233.08 At. % 24.49 3.13 57.06 13.44 1.88
Table 3. Chemical composition of oxides on the surface of 304 ODS sample 56 days SCW 550oC Energy level Fe2p3 Cr2p3 O1s N1s C1s Mo3d5 Binding Energy [eV] 711.63 573.82 531.34 398.89 285.85 233.38 At. % 6.62 0.58 42.32 4.65 43.41 2.42
For each element identified, the peaks were deconvoluted. After processing were identified three peaks corresponding to follows iron oxides: FeO, alfa-Fe2O3, and gama-Fe2O3, and two peaks for molybdenum corresponding to the oxides MoO2, and MoO3.
Figure 8. Wide-scan survey spectrum for 304 ODS sample, after 56 days of exposure in SCW at 550oC In figure 9 is presented XPS wide-scan survey spectrum obtained for a 304 L SS coupon exposed in supercritical water at 550oC for 56 days. The peaks of the chemical elements identified on the investigation surface and its composition on surface are presented in the table 4.
Figure 9. Wide-scan survey spectrum for 304 L sample, after 56 days of exposure in SCW at 550oC Table 4. Chemical composition of oxides on the surface of 304 ODS sample Energy level Fe2p3 Cr2p3 O1s C1s Mo3d5 Mn2p3 Binding Energy [eV] 711.38 577.31 531.16 285.72 233.34 641.98 At. % 7.33 2.20 46.32 39.47 3.25 1.43
After processing were identified three peaks corresponding to follows iron oxides FeO, alfaFe2O3 and gama-Fe2O3, and three peaks for chromium corresponding to metallic chromium, and to chromium oxides Cr2O3 and CrO3.
3.3 Oxide surface morphology The surface morphology carried out by TESCAN VEGA LMU scanning electron microscope. The secondary electron images have been acquired and processed by Vega TC software. The images of oxides developed on ODS exposed coupons revealed a rough and porous oxide morphology. The oxides formed are granularly and the size is dependent on time. After 10 days islands and rows of oxide crystallites is forming on the ODS samples (figure 10 a)). The crystallites have different sizes from zero to 6 microns. On the sample, can be seen both porous or compact islands. In same time on 304L sample arent present any visible crystallites at the same magnification (figure 10 b). In the figures 11 a) and b) is shown the oxide morphology developed on 304 ODS samples, respectively on 304L SS sample after 30 exposure days. For ODS sample large areas covered by oxides are visible, but on 304L SS sample, only some islands are visible. In figure 11b) can be observed the islands developed from grouping of small crystallites, which will increase later. After 44 days the oxides island developed on 304L SS are connected (figure 12 b), but crystallites with different shapes are visible. Ones have the straight edges and others have a rounded shape. These characteristics could be attributed to different oxide types.
a) b) o Figure 10. a) Oxide morphology at 550 C after 10 days on a) 304 ODS sample b) 304L SS On ODS samples after 44 days the morphology is changed (figure 12 a). Many crystallites containing cavities and small rounded non adherent crystallites appeared on the oxide surface. In figure 12 a) can be seen in few crystal tops, the forming of these rounded crystallites. At higher magnify (figure 13a) and 13 b) an oxide layer under the large crystallites and islands is visible. This layer contains smaller crystallites. In figure 13b) at 10000 magnify crystallites with different shapes and sizes can be visualized.
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a) b) Figure 11. a) Oxide morphology at 550oCafter 30 days on a) 304 ODS sample b) 304L SS
a) b) Figure 12. a) Oxide morphology at 550oC after 44 days on a) 304 ODS sample b) 304L SS
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a) b) Figure 13. a) Oxide morphology at 550oC after 44 days on 304 ODS sample a) x5000 b) x10000 3.4 Oxide cross-section chemical analysis To identify the oxides present on the samples the electron probe microanalysis have been performed. In figure 14 b) are presented the results of EDS line scan for iron, chromium, nickel, titanium, yttrium and oxygen and a secondary electron image, figure 14 a), of oxide sub-layers grown on a 304 ODS corrosion coupon exposed in supercritical water at 550oC for 56 days.
a) b) Figure 14. a) secondary electron image; b) EDS Line scan for Fe, Cr, Ni, Y, O in the oxide layer for 304 ODS sample (550oC, 56 days) The images suggest a stratification of oxide. An external iron oxide layer without chromium and nickel is followed immediately by a chromium oxide layer with minor iron content and by an enriched in nickel oxide layer close to metal/oxide interface. The oxide layer located adjacent to interface can be a spinel Fe, Cr, Ni oxide. It can observe the existence of a Y2O3 particles on the scan line (at 13 m position on the scan line).
The fluorescence profile from figure 14b) presents a chromium concentration increasing at middle of oxide layer with a corresponding decreasing in iron concentration. In figure 15 are presented EDS maps obtained for iron, chromium, nickel, oxygen, a composite map and a secondary electron image of oxide sub-layers grown on a 304 ODS corrosion coupon exposed in supercritical water at 550oC for 56 days. It can be observed the oxide layer stratification, the existence of three sub-layers. In the picture, the absence of chromium and nickel in the first sub-layer iron enriched is indicated. The outer layer is an iron oxide layer. Immediately under this layer an chromium enriched layer is present, and under this, at the metal-oxide interface is present an oxide layer enriched in chromium and nickel.
a)
b) Figure 15. EDS Maps for Fe, Cr, Ni, O in the oxide layer for 304 ODS sample (550oC, 56 days)
To confirm these observations, an other type of electron probe analysis has been performed. In few points, marked in figure 16, EDS multipoint analysis has been performed. The florescence spectra in each point was aquired and processed by Esprit software. The chemical compositions determined in each analysis point are presented in the table 5. The presence of the iron oxide in P1, P2 and P8 points are confirmed. In P3, P5 and P7 points is indicated the presence of an oxide enriched in chromium and nickel. The presence of yttrium oxide is proved in the P4 point. The composition of P10 point suggest the normal alloy.
Figure 16. A cross-section by oxide layer and EDS analysis points (304 ODS Sample)
Table 5. Chemical composition of oxides determined by EDS (SEM) in points from figure 11 Spectrum P1 P2 P3 P4 P5 P6 P7 P8 P9 P 10 O 5.40 12.40 5.10 10.63 6.78 4.63 7.14 12.45 9.40 0.02 Y 1.6 1.47 16.89 0.98 0.56 4.85 1.06 Ti 1.21 1.50 1.52 Cr 1.39 1.57 36.00 4.33 19.81 22.16 21.86 2.92 22.63 17.57 Mn 0.42 1.73 0.41 0.54 0.80 0.94 0.91 0.91 Fe 93.51 86.34 44.14 46.57 52.42 66.44 52.61 75.04 50.53 74.04 Ni 10.83 1.96 17.63 10.97 14.91 1.25 9.61 7.35 Cu 1.53 1.46 1.80 1.57 -
4. CONCLUSIONS The 304 ODS coupons exposed in supercritical water at 25MPa develop a rough and porous oxide morphology. The oxides formed are granularly and its sizes are dependent on time. Initially, islands or rows grow on the sample. Next the islands increase and become connected, extending on large areas. The next step is the forming the cavities or pores in the crystallites. On 304L stainless steel the oxides grow slower than ODS samples, at the end of experiments after 56 days, only few islands interconnected could be visualised. At higher magnifies an oxide layer with small crystallites can be observed under the large crystallites and islands. This layer contains smaller crystallites with different shapes and sizes. The XPS results suggest that if the oxide is thinner it contains more oxide types, iron, chromium and molybdenum oxides at the surface. When the oxide layer increases, the oxides arrange in layers, the iron oxides are maintained at the surface, and the chromium oxide sub-layer will increase under iron oxide. However the iron oxide layer is very thin, it contains three main oxides : iron(II) oxide FeO, iron(III) oxide alfa-Fe2O3 and iron(III) oxide gama-Fe2O3. When the oxide thickness increases, the FeO proportion decreases and Fe2O3 proportion increases. That is produced by iron oxide layering with forming of a Fe2O3 external layer and a FeO internal layer, or by forming FeO layer in the earlier stage of oxidation and afterward the formation of Fe2O3. EDS analyses indicated a stratification of oxide layer, three sub-layers can be observed: an iron oxides external layer, a median sub-layer enriched in chromium oxides, and an internal layer near metal-oxide interface containing nickel, chromium and iron oxides. Alloy fragments or metallic chromium, iron and nickel are encapsulated in the oxide layers. Acknowledgements This research was supported by RAAN - Institute for Nuclear Reasearch - Pitesti by Circuits Chemistry, Romanian National Reasearch and Development Program. The authors thank IAEA for financial support and to University of Beijing for providing the 304L ODS steel coupons for corrosion tests. 5. REFERENCES [1] Tae Kyu Kim, Chang Soo Bae1, Do Hyang Kim1, Jinsung Jang*, Sung Ho Kim, Chan Bock Lee and Dohee Hahn - Microstructural Observation and Tensile Isotropy of an Austenitic ODS Steel - Nuclear Engineering and Technology, Vol.40, No.4, June 2008, p 305-310. [2] Pantip Ampornrat, Gary S. Was - Oxidation of ferriticmartensitic alloys T91, HCM12A and HT-9 in supercritical water - Journal of Nuclear Materials 371 (2007) 1-17
THE DECOMMISSION AND UPGRADING OF TRITIUM LABORATORY FROM NATIONAL INSTITUTE FOR PHYSICS AND NUCLEAR ENGINEERING, MAGURELE C. Postolache, C. S. Tuta, Gh. Bubueanu, V. Fugaru, Diana Chiper
Horia Hulubei National Institute for Physics and Nuclear Engineering, P.O.B. MG-6, 077125, Magurele, Romania, e-mail: cristip@nipne.ro
ABSTRACT
The Tritium Laboratory from NIPNE, Romania has been commissioned as part of Radioisotope Research and Production Centre in 1976. The Tritium Laboratory is in the refurbishment process. A project POS Priority Axis 2 and several national research projects financially support the upgrading works, which involves dismantling of the used equipment and facilities. In this paper the preliminary refurbishment activities and reconstruction of new tritium laboratories are described as follows: -Radiological features for inventory of radioactive and non-radioactive wastes resulted from the cleanup activities -Decommissioning of the used equipments, radiochemical hoods and cleaning up of glove boxes and hoods - Characterisation and safety storage of resulted radioactive wastes - Designing and reconstruction of tritium laboratory - New equipments building or purchasing.
1. INTRODUCTION The Tritium Laboratory (TL) from NIPNE, Magurele has been commissioned as part of Radioisotope Research and Production Centre in 1976. At first, tritium laboratory were designed for synthesis of labelled compounds. Later, the activities were extended with tritium sealed sources obtaining, tritium detection and tritium wastes management researches. Since 2006, the TL is in the refurbishment process1,2. A several national research projects (3 CEEX, 2 NP, 6 PNCDI project and POS CCE/BCP 7PM/2008) were used as financially support to decommission and upgrading activities. Refurbishment Strategy The refurbishment of TL implied two main steps: (a) preliminary cleanup activities and (b) reconstruction and extension of the new TL (see Table 1) Table 1. The main steps of TL refurbishment Cleanup of old TL Upgrading Activities Period Activities Area measurements for inventory of radioactive 2009-2011 Feasibility study and non-radioactive wastes resulted from the refurbishment activities Dismantling and decontamination of the used 2009-2011 Designing of new TL equipment Decontamination of the radiochemical hoods 2010-2011 Re-construction and (RH) and glove boxes (GB) extension Removal of the apparent ceiling, utilities and 2011 New equipments paintwork from walls building or purchasing Characterization and storage of resulted 2010 radioactive wastes
100
Period 2005-2006
2007-2011 2011-2012 2007-2012
2. MATERIALS AND METHODS 2.1. Evaluation of Contamination in Tritium Laboratory The area measurements carried out in the old TL on 13 sampling areas (figure 1) by monitoring of the following parameters: - Determination of RSC - Determination of FC from samples of walls (paint and plaster), pavement and apparent ceiling - Determination of RSC from radionuclide fume hoods, glove boxes, functional and broken equipments. The determination of RSC has been carried out by smear test using polystyrene smears3 followed by the measurement of activity at Liquid Scintillation Counter (LSC). The determination of fixed and in depth contamination was performed by catalytic oxidation of samples using a RT Nabertherm Tube Furnace coupled at OS1700 Tritium Collector (figure 2). The collected activities are measured at LSC.
Figure 1. The distribution of sampling areas in the Tritium Laboratory
Figure 2. Sample oxidation system V-valve; C-Connectors; F-Funnel; S Sample; WS-Water Saturator; TC- Tritium collector
2.2. Decommissioning of Broken Equipments Tritium manifolds for synthesis of labelled compounds and respectively for obtaining of beta light sources, the facility for removal of labile tritium, the radio-chromatographic stand and endurance test facility were decommissioned. The components of facilities were cleaned up and radiological characterized. The components of vacuum pump were preliminary cleaned up using organic solvents. The components of glass, steel and aluminium were decontaminated using a sulpho-chromic solution followed by thermal treatment at 600C for 60 min at L X/11/B170 Nabertherm oven. The oven is provided with an air detritiation system (catalytic gases oxidation and desiccation cartridges). The radioactivity of the resulted liquid wastes was measured at LSC. 2.3. Boxes and Hoods cleaning up After decommissioning of facilities and equipments, the hoods and boxes were cleaned up using abrasive materials and selective solvents. The remained activity of cleaning materials was determined as FC using the protocol described in in the previous paragraph. The GB were kept in TL and used as tritium wastes storage area. The RH was decommissioned and temporary deposited in RPC area 2.4. Designing and reconstruction of Tritium Laboratory In cooperation with SC SILER TRAINING SRL Pitesti and CITON Magurele the new TL are designed by reconfiguration of old TL and extension of controlled area.
2.5. Dose Received by Workers. Personnel protective equipment like gloves, clothing and masks with tritium retention cartridge were used for less critical areas in the Tritium lab. Dose monitoring was another aspect of the protection of the personnel. During cleaning up activities the space area is monitored using 400SBDC Overhoff TGM and OS1700 Ortec Tritium Collector. The workers submitted regularly bioassays for evaluation of tritium concentration in bodies. 3. RESULTS 3.1. Evaluation of Contamination in Tritium Laboratory The radiological characterization of the rehabilitation areas carried out by evaluation of RSC and FC. The obtained results are shown in Table 2-5. Table 2. The total estimated RSC values classified on type of laboratory surfaces RSC Surface [kBq] LSC Laboratory walls 81.61 Walls in storage room 33.35 Walls in tritium laboratory 53.86 Apparent ceiling in entire laboratory room LSC Laboratory pavement Storage room pavement Tritium Laboratory pavement 31.60 13.88 33.35 273.96
Table 3. The total estimated RSC values classified on type of facility surfaces RSC Surface [kBq] GB and RH-external surfaces 92.12 GB and RH- inner surfaces 3274.24 Stainless steel radiochemical table external surfaces RCTI 32.41 SS radiochemical table inner surfaces 12.36 Radiochemical tableexternal surfaces 24.12 Radiochemical table inner surfaces 16.36 Stainless steel sink 8.74 Table 4. The total estimated FC values for different materials correlated with the radioactive wastes resulted after cleaning up of walls and pavement FC Area Volume of Radioactive Weight of Radioactive [kBq] [m2] waste [m3] wastes [kg] Wall paint 44.9 168 0.08 168 Plaster 699.5 168 1.68 3360 Pavement 462.1 110 0.55 1500 Apparent ceiling <3 110 2.5 275 Internal hood paint External hood paint
102
354.2 1.84
18 14.6
Table 5. Values obtained for RSC for old equipment from TL Analyzed Surfaces/facility Tritium manifold for labelled compounds synthesis with 1 U Bed-GB1 Tritium manifold for obtaining of beta light sources with 4 U beds-GB2 External surfaces of 3 delocated high vacuum systems GB2 oven external surface 2 GB2 oven internal surface 2 Furnace -GB2 external surface Glass labile tritium removal facility-GB3 Preliminary vacuum pump-GB3 Berthold TLC scanner Glass endurance testing facility-GB1 Recycling pumps and thermostats Activity [kBq] 5.64 7.85 34.67 76.89 247.35 24.35 4.23 424.21 124.68 148.74 126.35
3.2. Decommissioning of Broken Equipments In decommissioning activities the following elements have been removed: - 5 U Bed furnaces from 2 tritium manifolds - Glass resulted from tritium manifolds, facility for removal of labile tritium and facility for endurance test. - Stainless steel components of vacuum systems (AV 05 N&V) - Aluminum components from vacuum systems and TLC scanner - Steel from different equipments - Electronic components - Plastic, resulted from vacuum systems, facility for tritium removal and facility for endurance test - Liquid wastes (oil) After the first decontamination procedure of stainless steel components, the maximum value of measured RSC was estimated to 260 Bq/dm2. After chemical and thermal treatments, the RSC decreased at 314 Bq/dm2. The cleaned up components are stored in sealed plastic bags for future applications. Aluminum and steel components were preliminarily decontaminated at an estimated RSC of 280 Bq/dm2. Electronic components and plastics are stored for future processing by incineration. The radioactivity of the oils from vacuum pumps and liquid wastes resulted from cleanup process of decommissioned equipments was measured by LSC. Obtained results are shown in Table 6. Table 6. Liquid wastes resulted from decommissioning of used equipments Activity Resulted liquid wastes Volume [l] [MBq] 5.6 15603.9 Oil from preliminary vacuum pumps 0.3 2353.1 Oil from diffusion vacuum pumps 2 183.7 Organic solutions from decontamination 2 234.4 Sulpho-chromic solutions from decontamination 3.3. Boxes and Hoods cleaning up After cleaning up of GB and RH, the RSC of internal surfaces was determined.
- RSC values for GB are in range of 445 Bq/dm2; - RSC values for radiochemical hoods are in range of 7130 Bq/dm2. - The total weight of solid wastes was almost 8 kg with 783.76 MBq total activity (estimated using sample oxidation system) 3.4. Designing and reconstruction of Tritium Laboratory The structure of the new TL is shown in figure 3. The new TL has about 400 m2 area and contains: - Access corridor (~200 m2 surface) - High Radiological Risk Laboratory (HRRL), dedicated only for activities with tritium sources (~110 m2 surface) - Low Radiological Risk Laboratory (LRRL) for life sciences researches (~95 m2 surface)
Figure. 3. The structure of new Tritium Laboratory Architecture solution and utilities is summarised in table 7 Table 7. Architecture solution and utilities in new TL Architecture Access corridor and laboratories PVC carpet, Mipolan Esprit 500 type (Gerflor) pavement Access corridor and laboratories Steel plates covered with antistatic paint ceilings Corridor walls Aluminum sandwich panel structure covered with antistatic paint Laboratory and utility access doors Aluminum structure covered with antistatic paint Windows Aluminum covered with antistatic paint/ glass 4 mm thickness Laboratories walls Covered with Mipolan PVC foil with 1 mm thickness (Gerflor) Access lock chamber with 3 routes Aluminum covered with antistatic paint/ glass 4 mm thickness Utilities Electricity 2 power lines (220 V and 380 V / 200 kVA total power) UPS facilities for critical equipments (T NMR, LSC, HPLC, UVVIS, FTIR, etc) Plumbing 2 porcelain sinks in HRRL (only for personal cleaning) 1 porcelain sink (personal cleaning); and 1 stainless steel sink in LRRL (technological) Drains for potentially radioactively Existing technical solutions (LRRL) contaminated liquid effluents Each sources is provided with collection tanks (HRRL) VAC System Existing technical solutions Security Controlled access doors Intrusion detection and alarm facilities (broken glass detectors) Equipment and radiological facilities in TL is presented in Table 8
Table 8. Equipment and radiological facilities HRRL Tritium manifold (Tritec & Pfaiffer) and Labile tritium removal facilities Radio chromatograph HPLC (Agilent & Raytest) and Radio TLC (Raytest & Cammag) UV VIS (Analytic Jena) and FTIR ATR (Bruker Optics) spectrometers ESR Spectrometer (Brukler Biospin) LSC (PE) 2 Cryostats (DLK and Proline types) and high power chiller Preliminary and high vacuum pumps 4 new radiochemical hoods (Kotterman), 2 new GB (Jacomex) and 3 old GB 3 portable TGM (Overhoff), 1 T Surface Contamination Monitor LB1230 (Berthold) and 1 Tritium Colector (Ortec)
LRRL T NMR (Bruker Biospin) with high power UPS and oil free compressor Beta Imager (Raytest) Ovens, Incubator Freezer and bioassays storage container with liq. Nitrogen 3 old GB 4 old radiochemical hoods
3.5. Dose Received by Workers. The air contamination in TL area, determined using RS400-HTO Overhoff TGM, was lower than 74 kBq (2Ci)/m3. The exposed dose, evaluated with 400SBDC Overhoff TGM was lower than 5 Sv/h. The concentrations of tritium in the bioassays provided by operational workers were in range of 40 280 Bq/l. The tritium emissions in the environment, determined using OSI 700 Ortec tritium collector, was between 67 E+6 Bq/ winter moons and 78.5 E+6 Bq/summer moon for HTO and 4.8 E+6 and 4.83 E+7Bq /moon for T2/HT respectively. The derivate limits for tritium 1.33 E+9 Bq/year 4. CONCLUSIONS The TL has been commissioned in 1976 as part of Radioisotope Production Center. Since 2007 TL is in the process of refurbishment using as support several national researches projects. The refurbishment activities involved two main steps: clean up followed by designing and reconstruction/extension of new TL. The radiological characterization of the TL areas carried out by area measurements. Useless equipments and facilities have been decommissioned and temporary deposited in RPC area. Old GB were taken in TL and used as tritium wastes storage area and old RH were decommissioned and temporary deposited in RPC area. In the next step, new TL has been designed and upgraded; old 14-C laboratory is commissioned as part of new TL (LRRL for life science researches activities) New equipments have been purchasing or build. The new TL is designed to develop researches in the tritium detection, tritium wastes, tritium facility designing and testing, labelled compounds synthesis and radiation chemistry fields. REFERENCES 1. Lidia Matei, C. Postolache Tritium Laboratory with Multiple Purposes at NIPNE Magurele, Fusion Science and Technology, 54, (2008) 149-152 2. Lidia Matei, C. Postolache, Refurbishment of the Tritium Laboratory from NIPNE Romania, Fusion Science and Technology, 60, 3, (2011), 1021-1024 3. C. Postolache Lidia Matei, Evaluation of unfixed tritium surface contamination, Fusion Science and Technology, 48, (2005), 413-415
105
BEHAVIOUR OF FLUOROPOLYMERS IN PRESENCE OF TRITIATED WATER C. Postolache, Gh. Bubueanu, C. S. Tuta, V. Fugaru
Horia Hulubei National Institute for Physics and Nuclear Engineering, P.O.B. MG-6, 077125, Magurele, Romania, e-mail: cristip@nipne.ro
ABSTRACT
The behaviour of Polytetrafluoroethylene (PTFE), NAFION ionomer membranes and VITON fluoroelastomer in presence of high activity tritiated water (HTO) was analysed. Radiolytic stability of the fluoropolymers: HTO system was analysed by: (a) Simulation of radiolytic processes by quantum mechanical methods, (b) Simulation of radiolytic effects by exposure of fluoropolymers immersed in H2O at 60Co gamma radiation field, (c) Immersing of fluoropolymers samples in HTO with high activity for different time period. In both cases the samples were characterized by FT IR ATR, and fluoride ions emission from polymeric matrix. Keywords: tritium, radiolysis, computational chemistry, fluoropolymers
1. INTRODUCTION One of the most used methods for tritium recovery from tritiated water (HTO) or tritiated heavy water (DTO) relies on the combined techniques of Combined Electrolysis Catalytic Exchange and Cryogenic Distillation processes1. The electrolytic cell converts the tritiated water or tritiated heavy water into a mixture of hydrogen, deuterium and tritium. The mixture is purified and then tritium is recovered by catalytic isotopic separation technique. Tritium presence in the system induces an intense radiation field especially at the interface between the polymeric support and the aqueous solution2-4. Significant structural alterations of fluoropolymers with potentially negative effects can be identified. In this paperwork the radiolytic effects induce by presence of tritiated water / heavy water were studied. 2. MATERIALS AND METHODS 2.1. Simulation of radiolytic effects by quantum chemical methods For simulation of polymeric substrate behaviour in ionizing radiation field, in this study, olygomer structures with molecular masses between 1000 and 2500 Dalton were used. The simulation was realized on Intel Duo Core T6600 computer with 3 GB DD RAM using HYPERCHEM 4 and 6 computing software. For primary radiolytic effects evaluation was used an original model5: (a) molecules ionization by an electron release from highest occupied molecular orbital followed by molecule rearrangement for reaching the minimum energy value; (b) molecule neutralization by free electron capture from medium and fast molecule fragmentation without geometrical re-optimization. The chemical bonds predisposed to breakage due to radiolysis have minimum binding energy (BE). It is necessary to analyze the spatial distribution of molecular orbital to identify the molecule zones where energy absorption, respectively electron capture by ionizing molecule is happening. BE were determined by simulation of homolytic dissociation processes5. Radiochemical yields (G) were associated with the probability of homolytic fragmentation of chemical bonds. In this sense G represents the sum of individualized yields (Gi) for every chemical bond which is present in the LUMO orbital covering area. BE med (1) G = Gi = a x ALUMO ( i ) BEi
where: a is parameterization constant deduced from experimental data, BEi is bonding energy, BEmed is average BE for coverage area of LUMO orbital; ALUMO(I) is LUMO orbital covering grade on chemical bond, and x is weighting factor for protector effect of delocalized orbital. 2.2. Evaluation of absorbed doses at the interface fluoropolymers: tritiated water Due to the very low energy of -radiation emitted by tritium, the direct measurements of absorbed dose by the fluoropolymers using classical methods is practically impossible. For this purpose an evaluation model was developed6. A hemisphere represents the volume of tritiated water that irradiates the polymer surface. The radius of the hemisphere is equal with the maximal rate of -radiation emitted by tritium. The flow rate of absorbed dose is computed with the relation: d = .Em/m, where d = dose flow rate; = total radiation flux which interacts with the material surface; Em= main energy of tritium radiation and m = exposed material weight.
i = 60
i = i i yi
i=0 i =0
i = 60
(2)
Where: i = radiation flux emitted by tritium atoms of water volume circumscribed to two hemispheres; i = emission coefficient in effective angle (in direction of spot surface) at level of semispherical calotte; yi = attenuation coefficient in tritiated water stratum of radiation emitted by tritium from water volume circumscribed to two hemispheres surfaces and absorbed in tritiated water volume circumscribed of internal hemisphere surface. Based on previous presented data the value of dose rate can be calculated using the formula: 9,131 37 n 1022 i=60 2 i i / 5.77078 = n 24.25 Gy/ s d= 3 i + 3 i + 1 e 1 (3) 2 3m i =0 i +1 In this case, in function of volume concentration n, expressed in GBq/L can be calculated the value of dose flow rate.
2.3. Simulation of the tritiated water effects by exposure at gamma radiation field The PTFE, VITON and NAFION samples were exposed at 60Co gamma source which assure a 6.67 kGy/h dose rate. Samples weighting approximately 500 mg were introduced in 20 ml HDPE vials containing 10 ml ultra purified water, obtained using SIPLICITY UV MILLIPORE system. The conductivity was 0.3 S, with Total Organic Carbon (TOC) of 14 ppb. Absorbed doses, correlated with calculated value of HTO exposure (Matei Lidia, and al 2008), were 300, 450 and respectively 1000 kGy. 2.4. The samples exposure at tritiated water with high activity Tritiated water with high activity was obtained by isotope exchange technique 3T23 He:H2O7. HTO with initial activity of 45 GBq/mL has been purified by double distillation in quartz device. The dilutions were performed using ultra purified water. The fluoropolymers weighting approximately 500 mg were introduced in 4 ml HDPE vials containing 3 ml of HTO with radioactive concentration of 3.28 TBq/l. The samples were stored for 60 and 182 days respectively, at room temperature in a Glove Box. The total concentration of fluoride ions were measured in tritiated water. The samples was decontaminated by multiple washings with water, methanol and finally dried by storage for 24 hours in a vacuum desiccator. 2.5. Evaluation of radiolytic processes by IR spectrometry and fluoride emission The radio-induced fluoride release was studied by determination of pH and F- ions concentration using a WTW INOLAB MULTI 720 pH meter with F- selective electrode8. The
radiochemical yields were estimated by correlation between the obtained results, sample masses and absorbed doses. The radio-induced alterations of polymeric structures have been analyzed using IR spectrometry. In this study an FTIR ATR TENSOR 27 spectrometer Bruker type was used. The IR spectra for samples irradiated in a field, for samples exposed to tritiated water and for reference samples were collected and compared. 3. RESULTS 3.1. Evaluation of absorbed doses at the interface: solid surfaces-tritiated water solutions For radioactive concentration of 3.28 TBq/L the calculated dose rate is 79.52 10-3 Gy/s. On basis of dose rate is determined the value of 412 kGy for 60 days and 1250 kGy respectively for 182 days exposure at tritiated water. 3.2. Simulation of radiolytic effects by quantum chemical methods In case of PTFE, primary radiolytic effect simulation reveals a distinguish radio-sensibility of polymeric main chain. In case of geometrical optimized PTFE structures, in ionized state C-C BE manifests an important energetic decreasing from 268.77 kJ/mol, for neutral structure to 24.40 kJ/mol. Polymeric chain analysis in LUMO orbital zone shows a significant modification of C atoms stereochemistry, so C atoms have the conversion tendency of hybrid state from sp3 to sp2. This fact represents practically transition state in homolytic fragmentation of polymeric chain at CC bond level. In case of NAFION structure, modeling of primary radiolytic effect reveals a relative stability of PTFE backbone for those 2 structures (acid form and salt form). Radio sensibility of main chain is still low, because the energy decrease is not significant and LUMO orbital is distributed in sulfuric acid terminal zone. Hydrophilic structure presents reduced radiolysis stability; C-S, C-C and C-O are the most exposed bonds to fragmentation. Determined radiochemical yields present high value in a case of PTFE and an inferior value in NAFION case, but it reveal the tendency of hydrophilic groups losing. In VITON case, primary radiolytic effects simulation suggest higher stability in relationship with PTFE. LUMO orbital is located on main chain, at tetrafluoroethylene monomer unit. The F2CCF2 BE decreasing from 269.69 kJ/mol (for neutral structure) to 219.91 kJ/mol (in transitional state case). Because LUMO orbital covering grade on analyzed chemical bond have a small value, individualized yields (Gi) is not dominant like PTFE case. Radio sensibility of C-F and C-CF3 bound is still low, because the energy decrease is not significant and LUMO orbital is distributed in C-C main chain zone. In table 1 the radiochemical yields obtained values by simulation are shown. Table 1. Radiochemical yields determination by computational methods NAFION salt NAFION acid PTFE VITON A form form 0.038 G (C-F) 0.033 0.23 0.15 0.093 G (C-C main chain) 1.230 0.25 0.22 0.004 G (C-CF3) G (C-O) G (C-S) G (C-H)
108
0.23 0.32
0.22 0.25 0.004
3.3. Evaluation of radiolytic processes by IR spectrometry and fluoride emission 3.3.1. Evaluation of radiolytic processes by fluoride emission determination Determination of fluoride ions concentration from aqueous (H2O/gamma radiation and HTO) solutions reveals a higher stability of VITON and NAFION in relation with PTFE. The determined values of radiochemical yields for fluoride release (GF) were shown in Table 2. 3.3.2. Evaluation of radiolytic processes by IR spectrometry In PTFE case, experimental results (spectral analysis-figure 1) sustain simulation obtained results. Thus it was identified a specific band for unassociated carboxyl OH (3470 cm-1) and also trifluoroacetic acid (TFA) characteristic band (1780 cm-1, 1440 cm-1, 813 cm-1). In reference sample peaks from 2930 cm-1 and 2850 cm-1 domain are also present with a higher intensity and can be attributed to aldehyde C-H groups and the most probable to H-CF2-. In case of NAFION, IR spectral analysis (figure 2) is also in accord with quantum chemical simulation. The characteristics bands associated with vibration mode of C-O-C (980 and 968 cm-1) and SO3 (1320 cm-1, 1202 cm-1 and 1060 cm-1) were decreasing at dose between 100 and 1000 kGy. The high stability of PTFE backbone is confirmed also, C-F vibrations at 1200 cm-1 and 1144 cm-1 were unaffected. Table 2. Fluoride radio-induced emissions analysis from PTFE, NAFION and VITON samples
Sample PTFE:H2O PTFE:H2O PTFE:H2O PTFE:HTO PTFE:HTO NAFION:H2O NAFION:H2O NAFION:H2O
3.5 3.0 FxC-H aldehyd C-H >C=O OH carboxyl monomer
0.9 0.8 0.7 0.6
Dose [kGy] 1000 450 300 410 1250 1000 450 300
Release F / mass sample 4.66E-04 3.34E-04 2.64E-04 3.44E-04 4.58E-04 1.75E-04 9.00E-05 5.36E-05
G(F-) 1.75 2.79 3.31 3.16 1.38 0.66 0.75 0.67
Sample NAFION:HTO NAFION:HTO VITON:H2O VITON:H2O VITON:H2O VITON:HTO VITON:HTO
Dose [kGy] 410 1250 1000 450 300 410 1250
Release F / mass sample 8.48E-05 2.39E-04 3.07E-05 2.23E-05 1.96E-05 2.70E-05 3.96E-05
G(F-) 0.78 0.72 0.12 0.19 0.25 0.25 0.12
2.5
TFA
2.0
1 2
TFA
0.5 0.4
1.5
6 5 4 3 2 1
3500 3000 2000 1500 1000 -1 Wavenumber [cm ] 500
0.3 0.2 0.1 0.0
3 4 5 6
1.0
0.5 0.0
-0.1 3500 3000 2000 1500 1000 -1 Wavenumber [cm ] 500
Figure 1. IR spectra of unirradiated PTFE (1), gamma irradiated PTFE at 300 kGy (2), 450 kGy (3), 1000 kGy (4) and PTFE exposed at HTO for 2 months (5) and 36 months (6)
Figure 2. IR spectra of unirradiated NAFION (1), gamma irradiated NAFION at 300 kGy (2), 450 kGy (3), 1000 kGy (4) and NAFION exposed at HTO for 2 months (5) and 36 months (6)
109
The gamma irradiated VITON 1.2 sample IR spectra (figure 3) show 1.1 similar modification with irradiated 1.0 PTFE. We identified TFA characteristic 0.9 6 bands (1783 cm-1 superposed on 0.8 5 existing pick of reference sample, 1447 0.7 cm-1, 813 cm-1). The backbone 0.6 4 characteristic twins pick at 1170-1126 0.5 -1 3 cm present a small modification at 0.4 2 -1 0.3 1166-1129 cm with amplitude 1 0.2 inversion. 0.1 In case of samples exposed at 3500 3000 2500 2000 1500 1000 500 Wavenumber [cm ] high activity tritiated water, IR spectra are similar with gamma irradiated Figure 3. IR spectra of unirradiated VITON (1), gamma fluoropolymers at high absorbed dose. irradiated VITON at 300 kGy (2), 450 kGy (3), 1000 kGy (4) and VITON exposed at HTO for 2 months (5) and 36 months (6)
-1
1.3
4. CONCLUSIONS The behaviour of PTFE, NAFON and VITON fluoropolymers used in tritium recovery facilities from HTO or DTO was analyzed by followed methods: simulation of radiolytic effects by computational methods, irradiation of samples immersed in water with a 60-Co gamma source, and by storage in tritiated water with high radioactive concentration for 60 and 182 days. Exposed samples were analyzed by IR spectrometry and fluoride release analysis. In case of PTFE, used as isotope exchange support catalysts, quantum mechanical analysis evidence main chain homolytic fragmentation associated with HF and hydrophilic groups like OH and COOH formation. Radio-induced hydrophilic groups ponder is insignificant and does not affect polymeric support properties. HF formation is on the other hand significant and cannot be ignored. In NAFION case, used as a solid polymer electrolyte, quantum chemical analysis evidenced a higher stability in relation with PTFE. Two tendencies with lots of hydrophilic groups were identified: fragmentation of C-SO3 bonds and fragmentation of C-O and F2C-CF2 bonds from pendant hydrophilic sulfonate side chains. The fragmentation of every F2C-CF2 bonds was associated with HF emission. VITON fluoroelastomer, used at sealed device in tritium facilities, present higher stability at radiolysis in relationship with PTFE and NAFION. The determinant radiolytic process is fragmentation of CF2-CF2 bonds from main chain of polymer, but simulation obtained G values present low value. Experimental radio-induced changes are evaluated by IR spectroscopy and fluoride release determination. FTIR spectroscopy and fluoride release analyses are in accord with the quantum chemical simulation predictions. Obtained results suggest significant self-radiolytic processes in PTFE, NAFION and VITON fluoropolymers in presence of tritiated water. In authors opinion, fluoropolymers are not recommended to use as catalytic support, electrolytic cell membranes and sealed device applied for detritiation of water or heavy water. REFERENCES 1. Cristescu I, and al., Trenta Facility for Trade-Off Studies Between Combinated Electrolysis Catalytic Exchange and Cryogenic Distillation Fusion Science and Technology, 48, (2005), 97-101
2. Ionita Gh, and al, Endurance test for SCK-CEN mixed packing, proposed for water detritiation system at JET, Fusion Science and Technology , 48, (2005), 112-115 3. Matei Lidia, Postolache C, Radiolysis of polytetraflouorethylene and polystyrene catalytic supports in presence of tritiated water, Radiation Physics and Chemistry 76, (2007), 12571262 4. Matei Lidia, Postolache C., Cristescu I., Brad S, Behavior of Nafion perfluorosulfonate ionomer membranes in presence of tritiated water, Fusion Science and Technology, 54, (2008), 475-478 5. Postolache C., Matei Lidia, Evaluation of fundamental processes in macromolecular structures radiolysis using quantum-chemical methods, Radiation Physics and Chemistry, 76 (2007), 1267-1271 6. Postolache C., Matei Lidia, Ionita Gh., Behavior of Hydrofobic Isotopic Exchange Catalysts in the Presence of Tritiated Water, Fusion Science and Technology, 48, (2005), 688-691 7. Matei Lidia, and al, Synthesis of Labeled Compounds using Recovered Tritium from Expired Beta Light Sources, Fusion Science and Technology, 54, (2008), 643-646 8. Matei Lidia, C. Postolache, C Tuta, S Brad, Facility for Endurance Testing of Hydrophobic Isotope Exchange Catalysts, Fusion Science and Technology, 60, (2011), 1419-1422
RESEARCH PROGRAM OF ICIT ON TRITIUM FIELD AS SUPPORT FOR FUSION PROGRAM Marius Valentin Zamfirache, Anisia Mihaela Bornea, Ioan Stefanescu, Carmen Varlam, Nicolae Bidica
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250/732744; fax: 0250/732746; E-mail: mariusz@icsi.ro
ABSTRACT
Institute for Cryogenic and Isotopic Technologies (ICIT) Rm.Valcea has built an experimental pilot plant having as the main objective the development of a technology for detritiation of heavy water processed in CANDU-type reactors at the nuclear power plant in Cernavoda, Romania. Within ICIT were developed laboratories that cover a wide area of investigations in the field of tritium research, which enabled ICIT to be part of the detritiation technology group for ITER. There are also a number of support activities and a tritium research program which are presented as an overview of the ICIT new research tasks. This work is focused on the presentation of ICIT research activities, perspectives and its capability related to water detritiation technologies and also to the development of research on issues in the field of nuclear fusion. Keywords: Tritium, fusion, detritiation, heavy water.
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COLD NITROGEN RECOVERED USE TO INCREASE PERFORMANCE IN THE CRYOGENIC PILOT PLANT PURIFICATION MODULE Gheorghe Popescu, Sorin Gherghinescu, Ionut Spiridon, Marian Vacaru
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, code 240050, Str. Uzinei 4, OP Raureni, CP 7, Valcea, Romania, Phone: 0040 250 736979, fax:0040 250 732746, e-mail: popescu.gheorghe@icsi.ro
ABSTRACT
Deuterium and Tritium Separation Pilot plant aims to demonstrate and develop the technology of tritium extraction from tritiated heavy water provided from the moderator circuit of CANDU reactors (CANada Deuterium Uranium, PWR). One of the technological process phase is the gas (D+T) drying, resulting from isotopic exchange column (LPCE) in order to separate the tritium in the cryogenic distillation (CD) module, avoiding the risk of an ice cap. Final drying is done in two 13x molecular sieve (Na2O Al2O3 2SiO2 nH2O) adsorber which retains molecules with diameters less than 0.9 nm, preferably polar molecules; water fits in both requirements and can be removed up to a dew point of -100C. Before reaching the maximum adsorption capacity it must be started the first adsorber regeneration phase and the gas will further pass through the second adsorber. The problem we have here is cooling the adsorber metal body in a short enough period of about 2-4 hours; molecular sieve is cooled with a dry deuterium gas flow extracted from the cryogenic distillation module. Since at high temperature the thermal conductivity of the sieve is bigger it becomes obvious that it can not be cooled without prior or at least simultaneous metal casing cooling. In respect to that we made a forced cooling system for the adsorber using two coils made of copper tube with inner diameter of 8 mm and a unfolded length of 47m. The refrigerant used was cold nitrogen coming from the liquid nitrogen storage tank (99.999%, 1.06ppm O2, <3ppmH2O) with a flow rate of 1.5m3/h, corresponding to the normal evaporation rate, and a pressure of 1.3bar. Temperature values were determined using K type thermocouples and infrared thermography was used both for spot measurements of surface temperature and also for the heat transfer uniformity observation. The experiment was successful and the adsorber cooling time went to 2 hours for a temperature of 16C in the warmest point, which is almost 10 times faster than previous. The reserve of time so created can be used to increase the adsorption capacity by lowering the molecular sieve temperature even further, up to 10C, thus increasing the efficiency of the plant purification system. Keywords: Cold nitrogen, molecular sieve, cooling system, adsorbtion capacity, tritium separation.
3D SIMULATION OF A DEUTERIUM STORAGE SYSTEM Eusebiu Ionete1, Bogdan Monea1, Roxana Ionete1, Christoph Plusczyk2
1
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, code 240050, Str. Uzinei 4, OP Raureni, CP 7, Valcea, Romania, Phone: 0040 250 736979, fax:0040 250 732746, e-mail: bogdan.monea@icsi.ro 2 Institute for Technical Physics, Tritium Laboratory, Karlsruhe, Germany
ABSTRACT
A three-dimensional (3D) modeling to simulate the adsorption of deuterium on a cylindrical storage vessel with sponge Titanium bed was developed. The mathematical model that describes the absorption process consisting of differential equations for the system (energy, mass and momentum) and the ones referring the kinetics of adsorption was numerically implemented. 112 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
N Nu uc ea ar Po er na an nd df us n cl le rP ow we r f fi is ss si io on fu si io on The model was applied to a reactor in the shape of a cylindrical container filled with sponge titanium and having 50 mm height and 30 mm diameter. The region filled with Titanium sponge was 20 mm height and the free space 30 mm. To describe the dynamic process taking place in the reactor, the flow and heat transfer theory of porous media have been applied. The absorption speed is in close relation with the activation temperature and pressure. The simulation results indicated that the pressure drop is not uniform during the absorption. This fact is not easy deductible from the experiment because of the relative spatial location of the pressure gauge. In the bed region, between titanium clusters the pressure varies spatially to the bottom of the vessel. The reactor was modeled by using symmetry properties and the mesh was created using tetrahedrons method containing a number of nodes and cells. The numerical simulation model is based on SIMPLE (semi-implicit method for pressure linked equations) algorithm. Keywords: mathematical model, deuterium, adsorption, titanium sponge
PROPAGANDISTIC VERSUS PROBABILISTIC RISK LEVEL OF ACCIDENTS IN NUCLEAR SAFETY ANALYSES Gheorghe Florescu1, Ioan-Bogdan Florescu2
1
Institute for Nuclear Research, Pitesti, ROMANIA, gheorghe.florescu@nuclear.ro 2 University of Pitesti
ABSTRACT
The high generation of power production technologies are planned and designated to solve the actual civil and industrial requirements demanding to eliminate the existing problems related to energy delivery price and efficiency; also to avoid the environmental disastrous impact of abnormal nuclear events. Commonly these nuclear technologies are reported to be modern, progressing, improved or new. NPPs safety systems availability is necessary to be continuously monitored, supervised and improved; in the same time the safety of the nuclear energy production needs surveillance for level preservation and increasing. Actual development of new materials and efficient technological processes offers the possibilities for adequate implementation and use of them in the NPPs system structures, configuration, functioning and operation. The new industrial technologies and the actual scientific discoveries, also the international cooperation, offers the opportunities to preserve, protect and strengthen the actual safety barriers in order to cumulate and use advanced energy production processes to efficiently use of the new energy sources; to build improved, reliable and safety power plants. In the paper are presented original concepts and elements related to calculation of accidents risk level and differences between propagandistic (misinformed - virtual or false) risk level and probabilistic (real) risk level. The paper also presents study elements related to existent latent risk (versus the calculated and real risk level) for accidents taking into account the hidden weaknesses that exist in the new NPPs design and nuclear energy production technologies. In this respect are performed - and briefly presented - significant risk evaluation studies that use: adequate NPP systems models; predefined and analysing appropriate reliability data. Keywords: nuclear safety, probabilistic, propagandistic, accident risk, nuclear power
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Hydrogen and Fuel Cells
H Hy dr ge en n a an nd d F Fu ue el el yd ro og l C Ce ll ls s
HEAT TRANSFER MODELLING OF STEAM METHANE REFORMING Elena Carcadea, Mihai Varlam, Ioan Stefanescu, Mihai Culcer, Mariana Iliescu, Enache Adrian, Vasile Tanislav, Catalin Capris
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250.732.744; fax: 0250.732.746; E-mail: lili@icsi.ro
ABSTRACT
In this paper a heat transfer modeling of a membrane reactor for methane steam reforming was developed in order to analyse the importance of temperature for methane conversion and hydrogen yield. A CFD softwarwe was applied to analyze the steam methane reforming in the chemical reactor investigated. Also, the study was intended to give us an insight regarding the interaction between the flow, chemical reaction and temperature. Keywords: heat transfer modeling, reactor, methane reforming.
COMPOSITE NAFION/TiO2 MEMBRANES FOR PROTON EXCHANGE MEMBRANE FUEL CELLS D. Ebrasu1, G. Dorcioman2, E. Axente2, I.N. Mihailescu2, L. Patularu1, D. Schitea1, M. Varlam1, I. Stefanescu1, L.M. Constantinescu3
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0040 250 732 744, fax: 0040 250 732 746, E-mail: daniela.ebrasu@icsi.ro; 2Lasers Department, National Institute for Lasers, Plasma and Radiations Physics, 409 Atomistilor Street, PO Box MG-54, RO-77125, Magurele, Ilfov, Romania, 3Bucharest University-Faculty of Physics, Atomistilor Street no. 405, PO Box MG-11, Magurele, Ilfov, Romania
1
ABSTRACT
Nafion/oxide composite membranes were produced by pulsed laser ablation method using UV laser pulses generated by a COMPEXPro 205 KrF* excimer laser source = 248 nm and FWHM 25 ns. We selected TiO2 material and distributed it uniformly over the surface of Nafion 112 membrane using 100 and 250 laser pulses and an incident laser fluence set at 5 J cm2 were applied to improve the water retention property and corresponding proton conductivity under high temperature operating conditions. TGA and DSC methods were used to characterize the thermal stability of the membranes. Furthermore, UV-Vis spectroscopy experiments showed incorporation of the inorganic phase in the polymer matrix. Water uptake and proton conductivity characterizations of the Nafion composite membranes were carried out, and the results demonstrated that there was higher water uptake and an increased proton conductivity at 120 C temperature, compared with Nafion 112 membrane. Keywords: Nafion; composite membrane; PEMFC
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MATHEMATICAL MODELING OF CATALYTIC HYDROGENATION PROCESS OF GLYCEROL TO PROPYLENE GLYCOL Adriana Marinoiu1, Claudia Cobzaru2, Elena Carcadea1, Vasile Tanislav1, Catalin Capris1
1
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0040250732744, fax: 0040250732746; 2Gheorghe Asachi Technical University of Iai, Faculty of Chemical Engineering and Environmental Protection, D. Mangeron, 71, 70050
ABSTRACT
The conversion of glycerol hydrogenolysis in aqueous solutions on a commercial copper chromite catalyst is evaluated under various conditions of temperature and time. These parameters are necessary and sufficient for developing a mathematical model of the hydrogenolysis process. This model shows a good arrangement of the experimental points on the response surfaces and a correlation coefficient closed to unity. Keywords: copper chromite catalyst, hydrogenolysis, mathematical model
EXPERIMENTS REGARDING THE EFFECTS OF ISOTOPIC SEPARATION IN PEM ELECTROLYSERS Mariana Iliescu, Mihai Varlam, Roxana Elena Ionete, Mihai Culcer, Mihai Balan
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no.4; P.O. Box 7 Rureni, 240050, Rm.Vlcea, Romania
ABSTRACT
The paper deals with the first experiments conducted in the National Center for Hydrogen and Fuel Cell, in order to reveal the isotope separation effect in water electrolysis. Four water compositions having deuterium content in the range of natural (144 ppm) to 2%, were used to feed a PEM electrolizer, and the deuterium content of the evolving hydrogen was analyzed, revealing a slightly depletion. Keywords: PEM electrolyzer, water electrolysis, isotope separation
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PARAMETRICAL STUDY OF STEAM METHANE REFORMING IN A MEMBRANE REACTOR Elena Carcadea, Mihai Varlam, Ioan Stefanescu, Adriana Marinoiu, Vasile Tanislav, Catalin Capris
1
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0040250732744, fax: 0040250732746
ABSTRACT
The aim of this paper is the parametric investigation of methane steam reforming to synthesis gas in a membrane reactor. Steam methane reforming in a membrane reactor is investigated in this paper using ANSYS Fluent software. The influence of some parameters on mass and heat transfer is analyzed. Thus, the influence of pressure, inlet temperature from the reforming area and velocity of the sweep gas was considered. Two domains were taken into account in our simulation (reforming and permeating areas) while the membrane was considered one dimensional. The simulations carried out intended to establish the maximum value of temperature in the sweep area of the porous membrane reactor, close to the inner permeation tubes, because a 450C maximum value of temperature is required for long life and maximum performance of these tubes. Also, an optimum velocity for the sweep gas and an optimum pressure in the reforming area was searched by simulations carried out.
NEW CONCEPTUAL DESIGN FOR PEM FUEL CELL Anghel Vasile

National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0040250732744, fax: 0040250732746
ABSTRACT
PEM Fuel cells convert chemical energy directly into electrical energy with high efficiency and low emission of pollutants. Before as PEM fuel-cell technology can gain a significant share of the electrical power market, important issues have to be addressed. These issues include optimal choice for PEM fuel cell design, and the development of alternative materials in the fuel-cell stack. In this work, a three-dimensional model is used to analyze the important interaction effects solved using a nite element method and adequate simulation software. The factors considered are channel width, shoulder width, gas distribution electrode (GDE) thickness, GDE conductivity, GDE porosity, and new materials for simulation stack design. The new stack PEM fuel-cell prototype use innovative alternative materials selected less than 5 years ago, and for conceptual design is take into consideration integrated engineering and the cost and durability is analyzed. Keywords: Design, PEMFC, reliability, FEM
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OVERVIEW ON RENEWABLE ENERGY SOURCES HYDROGEN PRODUCTION USING THE ELECTROLYSIS PROCESS M. Balan, M. Culcer, I. Iordache, L. Patularu, A. Ciocan
National Institute for Research and Development for Cryogenics and Isotopic Technologies- ICIT Rm. Valcea, 4 Uzinei St.,240050
ABSTRACT
Water electrolysis is the easiest and most efficient method of obtaining hydrogen. The advantages of this process consist in obtaining high purity hydrogen with a reduced impact on the environment, but on the other hand, in order to reach a high efficiency, it needs to be linked with renewable energy sources. Proton exchange membrane (PEM) electrolysers are much more adequate for integration with renewable energy sources, compared to alkaline and solid oxide electrolysers due to their structural and functional characteristics. The current paper presents a brief overview of the potential electrolysers and renewable energy sources have in ensuring the transition towards a hydrogen economy, a short comparison between PEM and alkaline electrolysers and a small scale renewable energy sources hydrogen production installation that validates the concept. Keywords: hydrogen, electrolysis, PEM, alkaline, renewable energy sources
1. INTRODUCTION Throughout the whole world, the current energy market is still dominated by fossil fuels which are present on the planet as a limited resource. Facing the imminent danger of a major energy crisis, caused by the depletion of fossil fuel resources and their ever increasing price, the current society had to understand that new methods of producing energy were required in order to smoothen out the transition towards a modern society in which energy will cease being a scarce resource. Hydrogen plays a major role in the transition towards a modern energy system, as an alternative energy carrier along with electricity. This will of course lead towards an accelerated development of all hydrogen related technologies in the near future, starting with the methods of obtaining hydrogen. While there are various methods of producing hydrogen, one of them stands out due to its huge potential of being linked with renewable energy sources: electrolysis. Compared to methane reforming, obtaining hydrogen from electrolysis is a far more expensive process mainly because of the high quantities of energy required. However, if the electrolysis process is supplied with the surplus energy produced by renewable energy sources, it suddenly becomes a much more attractive technology that has a huge potential to evolve hand in hand with the transition towards a new energy economy. 2. PROTON EXCHANGE MEMBRANE AND ALKALINE ELECTROLYSERS At the moment there are numerous types of electrolysers used for hydrogen production, classified depending on the electrolyte they use and their working temperature: proton exchange membrane (PEM) electrolysers, alkaline electrolysers and solid oxide electrolysers. Solid oxide electrolysers operate at temperatures above 800 C and will not make the object of our further discussion in which we will present a brief overview of PEM and alkaline electrolysers and a comparison between these two.
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2.1. PEM electrolysers The evolution of proton exchange membrane (PEM) electrolysers is directly linked with the synthesis and usage of proton conducting polymer membranes. The key characteristic of PEM electrolysers is represented by the use of a solid electrolyte that allows cation transfer due to hydration and acid groups contained in the structure of the polymer. The polymeric membrane also has the role of separating the two generated gases at the two electrodes. PEM electrolysers are relatively easy to build and operate because they are compact and dont contain corrosive liquids. One of the key features of PEM electrolysers consists in the fact that they are adaptable to small scale applications, capable of providing as low as 0.01 Nm3/h H2. On the other hand, due to their modular construction, the output capacity can scale up to 70 Nm3/h H2 and even higher in specific applications. The normal operating pressure of a PEM electrolyser is around 15 bar, while the energy efficiency varies between 5 and 7 kWh/ Nm3 H2, with the current density exceeding 1 A/cm2. This type of electrolysers can work at relatively high pressures, up to 500 bar and this leads to discovering a new advantage over other electrolysis systems: there is no need for complicated hydrogen compressing systems. Compared to alkaline electrolysers, proton exchange membrane electrolysers work at high current densities, which makes them suitable for special applications where space is a limited resource. Nafion membranes, made by DuPont, represent the common membranes for PEM electrolyser applications and while they can be considered the central element of such systems, they are also a weak link due to their high price. Note that Platinum and Ruthenium, used for the catalyst, also add to the price, making PEM electrolysers an expensive solution.
Figure 1. PEM electrolyser operating principle 2.2. Alkaline electrolysers Historically speaking, alkaline electrolysers were the first ones developed for producing hydrogen using this process, starting with the 1920s. At first, this type of electrolyser was used in facilities that had the goal of maximizing the efficiency of hydro power plants and are still used today at small, medium and large scale. The energy efficiency of alkaline electrolysers is situated between 4 and 6 kWh/ Nm3 H2 and at the moment they have an output range between 10 and 100 Nm3/h H2. Hydrogen purity in alkaline electrolysis installations is situated around 99.8% and can go up to 99.999% with the help of additional auxiliary purifying facilities. One of the key advantages of alkaline electrolysers in comparison with other types currently available on the market consists in their reliability and their life cycle which can be measured in
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decades, rather than years. Alkaline electrolysers imply the use of alkaline solutions, especially potassium hydroxide 25-30 % as the electrolyte that ensures the anion transfer process. The current density in an alkaline electrolyser varies between 0.2 and 0.4 A/cm2, while the operating pressure is situated between 1 and 30 bar. Another key feature of the alkaline electrolyser consists in the fact that it does not require expensive Pt or Ru catalysts and can work well with Ni based catalysts. In terms of costs and economy, this is a huge advantage of alkaline electrolysers, especially when taking in to consideration large scale applications. On the other hand hydrogen and oxygen producing installations that contain an alkaline electrolyser require a considerable amount of auxiliary equipment. Electric installations, alkali solution recycling installations, compressing and transport utilities, water treatment and gas purifying equipment, all of these are necessary for an efficient electrolysis process.
Figure 2. Alkaline electrolyser operating principle Table 1. PEM vs. Alkaline electrolysers PEM electrolyser Alkaline electrolyser High current density Low current density Can operate at high pressure Lower operating pressure Large range of operating pressure Requires maintenance Produces pure water Lower water quality Fast response time Slower response time Compact structure Less compact structure Accessible mass production due to simple Difficult to obtain small scale systems structure Allows small scale systems More difficult mass production Uses expensive catalysts Cheaper materials, but high Cheap installation installation costs Moderate H2 production cost High H2 production cost High reliability Long life cycle Contains corrosive liquids
Operation
Construction and costs
Safety and reliability
3. RENEWABLE ENERGY SOURCES HYDROGEN PRODUCTION Providing the necessary energy for the electrolysis process from renewable energy sources is the most accessible solution at the moment for overcoming the main disadvantage of this hydrogen producing method: the high production costs due to the high energy demand. This would not only help achieve a better economic efficiency, but it has the potential of helping the future so-called
hydrogen economy become eco-friendly by obtaining the necessary hydrogen without unwanted emissions caused by the burning of fossil fuels. In order to validate the theory that hydrogen can be obtained from renewable energy sources with the technology and equipment currently present on the market, we have set up a proof of concept installation at the National Center for Hydrogen and Fue l Cell. The central piece of our installation is the HOGEN HP 40 Hydrogen Generator built by Proton, a proton exchange membrane (PEM) on-site hydrogen generator with a net production rate of 1.05 Nm3/h H2, which translates in to 2.28 kg H2 every 24 hours. The PEM hydrogen generator is able to deliver gas at a 99.9995% purity and a nominal pressure of 165 bar, meaning that there is no need for an additional compressor for transferring H2 in high pressure tanks. The required water input is situated at 0.94 liters per hour at a pressure between 1.5 and 4 bar. A very important feature of the HOGEN HP 40 Hydrogen Generator consists in the fact that it can be powered from a 220 V outlet, making it adaptable to almost any type of application, especially small and middle scale ones. The whole system is air cooled, meaning that additional components necessary for a liquid cooled system are not necessary. The energy demand of the PEM electrolyser is delivered by the renewable energy system that has two major components: a PV array and a vertical axis wind turbine. The PV array consists of 28 SHARP NU-180E1 photovoltaic modules, each having a rated power of 180 W at standard testing conditions. The eddy UGE 600 vertical axis wind turbine has a rated power of 600 W, achievable at a wind speed of 12 m/s, but it delivers energy to the system as soon as the wind speed exceeds 3.5 m/s. Another key element of the whole renewable energy sources hydrogen production installation are the two SMA Sunny Island 5048 inverters, stacked in parallel in order to provide the hydrogen generator with the necessary power. Each one of them has a rated power of 5000 W and the interesting part about them is the fact that they are able to support both DC and AC input, meaning that they can be supplied with energy from batteries and from the grid.
Figure 3. Renewable energy sources hydrogen production diagram Summing the rated power of all the renewable energy production sources available still does not cover the energy demand of the hydrogen generator, forcing us to use a more complicated system that includes a stack of batteries and two smart inverters that allow energy input from the grid whenever there is not enough energy in the battery stack to supply the hydrogen generator. With the use of the intelligent control system of the hydrogen generator, the whole system is able to function continuously, whether or not the energy demand can be covered by the PV array and wind turbine. 4. CONCLUSIONS In order to sustain the transition towards a hydrogen economy that will reduce the impact of fossil fuels over the energy sector and environment, the electrolysis process has to be developed and adjusted in search for the best efficiency and adaptability. Whether we are talking about PEM,
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alkaline, solid oxide or new electrolysis methods, the goal is to obtain the needed quantity of hydrogen, with the necessary purity, with low resource consumption and the lowest possible impact on the environment. The proton exchange membrane electrolysis process is perfectly suitable for integration with renewable energy sources, being part of the chain that can represent an alternative to traditional energy production systems. However, in order to achieve the best possible efficiency, it would be wise to power the electrolysers with the surplus energy produced by renewable energy sources, surplus that would otherwise be lost. Large scale electrolysis installations have the potential of being operated in areas with high density of renewable energy sources, for example large wind turbine compounds that have recorded a significant expansion in the last several years. This will not only raise the overall efficiency of the whole process, but will also help balancing the energy distribution grid. The renewable energy sources hydrogen production installation presented in this article is at the moment nothing more than a proof of concept that has been validated inside our laboratory. The process discussed above is a small part of a much larger system that can also include other types of renewable energy sources (for example small scale hydro), a hydrogen vehicle charging station and fuel cells, in order to provide a complete solution for a small to medium residential application. BIBLIOGRAPHY 1. I. Iordache, I. Stefanescu, Obtinerea hidrogenului Metode si procedee, Editura AGIR, 2011 2. J. Ivy (National Renewable Energy Laboratory), Summary of Electrolytic Hydrogen Production, DOE Hydrogen Program, NREL/MP-560-36734, 2004 3. National Research Council and National Academy of Engineering, The Hydrogen Economyu Opportunities, Costs, Barriers and R&D Need, The National Academies Press, 2004
ELECTROCHEMICAL CHARACTERIZATION FOR DIFFERENT TYPES OF GRAPHENE SUBSTRATES Ana-Maria Ducu, Stefan-Marian Iordache, Catalin Ceaus, Laurentiu Popovici, Adriana Balan, Ioan Stamatin
University of Bucharest, Faculty of Physics, 3Nano-SAE Research Center, Bucharest-Magurele, Atomistilor 405, M.G.38, tel.0214574838, e-mail:office@3nanosae.org
ABSTRACT
The purpose of this paper is to investigate the electrochemical response of different graphenic substrates, obtained in our laboratory via solvothermal method, in an acidic media. Electrochemical investigations are important in catalyst chemistry, the relationship between structure and activity having a major impact in our understanding of the catalytic process. We chose perchloric acid as supporting electrolyte and all measurements were conducted in a three electrode Teflon cell. The cyclic voltammetries indicated a thinner double-charged layer for graphene, while the response for platinum decorated graphene showed a broad reduction pick for oxides species, shifted to more negative potentials. The different methods of exfoliation and preparation of the graphenic substrate induce a specific character in the substrate, character observed in the shape of the voltammograms. 124 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
Environmental and Life Quality
E nv nm en nt al an nd dL eQ ua al En vi ir ro on me ta la Li if fe Qu li it ty y
LIFE AND ENVIRONMENTAL PROTECTION BY DEVELOPING NEW INNOVATIVE SOLUTIONS FOR THE SAFETY OF BUILDINGS, SYSTEMS AND EQUIPMENT TO VIOLENT SEISMIC MOVEMENTS (EARTHQUAKES) Viorel SERBAN1, Adrian PANAIT1, Madalina Angela ZAMFIR1, George Alexandru CIOCAN1, Marian ANDRONE1, Laura Elena SERBAN2, Liviu Dan POSTOLACHE2, Viorela Maria POSTOLACHE2
Subsidiary of Technology and Engineering for Nuclear Projects, Str. Atomistilor, no. 409, Magurele, Romania, e-mail: serbanv@router.citon.ro; 2SC SIGMA PATENT STUDIO SRL, Bucharest, Romania
1
ABSTRACT
The environment and population are subject to slow and fast action events generated by phenomena dependent or independent of human action. Among violent actions which affect the environment through loss of property and human lives are earthquakes. Because violent seismic movements cant be controlled by man, protection from such events can only be made by innovative technical solutions to ensure reduction of the dynamic response of constructions, equipment and pipeline networks to repeated seismic action. The new solutions must be designed so that they can be applied to new structures and to increase the degree of resistance to existing structures. The paper presents new types of mechanical devices developed by SITON and SIGMA SS companies in cooperation with other units in Romania, by means of which to control, limit and damp shocks, vibrations and seismic movements in buildings, equipment and pipe networks. The new devices, called SERB-devices can overtake large static loads over which dynamic loads may overlap and be damped. The devices allow cutting-off the dynamic action in-coming from the environment to the protected systems (building, equipment, pipe network, etc) and the overtaking of shocks and vibrations generated by the systems to protect the environment. Keywords: shocks, vibrations and seismic movement, control, limitation, damping, base isolation systems.
ENVIRONMENTAL PROTECTION BY DEVELOPING EFFICIENT SOLUTIONS FOR THE COLLECTION, STORAGE AND REUSE OF RENEWABLE ENERGY Viorel SERBAN1, Adrian PANAIT1, Madalina Angela ZAMFIR1, George Alexandru CIOCAN1, Marian ANDRONE1, Laura Elena SERBAN2, Liviu Dan POSTOLACHE2, Viorela Maria POSTOLACHE2
Subsidiary of Technology and Engineering for Nuclear Projects, Str. Atomistilor, no. 409, Magurele, Romania, e-mail: serbanv@router.citon.ro; 2SC SIGMA PATENT STUDIO SRL, Bucharest, Romania
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ABSTRACT
The main cause of environmental degradation results from intensive and inefficient exploitation of carbonbased energy, imposed by industrial development based on less advanced technologies. Following this exploitation the share of greenhouse gases has increased having as consequence global warming and devastating weather phenomena. The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 127
E nv nm en nt al Pr ec n. .I nd du us al Ri En vi ir ro on me ta lP ro ot te ct ti io on In st tr ri ia lR is sk k The only solution that can now reduce this effect is efficient exploitation of renewable energy (hydro, solar, wind, waves, marine currents, bio, etc.) combined with storage solutions and reuse of energy. The SERB solar-wind-hydro-wave-ocean stream-bio power plant with storage and reuse energy to increase the efficiency of renewable energy (SERB RPP-01) and the possibility to set the load curve of the electrical power system presented in this paper is an efficient solution to exploit renewable energy potential including sites with low and average energy potential. The plant is constructed of a central module which allows the storage and reuse of energy and of several specialized modules, based on the potential of renewable energy in the location. SERB RPP-01 could be an important component for the efficient use of the renewable energy, all over the word, to achieve the aim of the Set -Plan and RES Directive 20/20/20 and for the implementation of the Smart cities concept. Keywords: solar-wind micro power plant, renewable energy, solar, wind, energy storage, control
1. INTRODUCTION Economic growth generated in particular by the industrialization has the negative effect of consistently increasing the degree of environmental pollution. One of the important consequences of increasing the environmental pollution is that climate change is due to the increase in greenhouse gases in the atmosphere. The share of electricity and heat has a maximum contribution in the generation of greenhouse gases released into the atmosphere. [1] Heat and electricity production, now and in the near future is made by burning fossil fuels, a process that generates solid and gaseous pollutants as well as nuclear fission reactions of uranium and thorium which produce radioactive waste with very high half-life time and which in case of accidents, can radiologically infest large areas with long-term negative consequences. Currently, the whole world is dependent on fossil fuels in terms of energy. Turning primary energy into electricity is accompanied by combustion processes that produce a high environmental pollution and greenhouse gasses. Energy demand increases every year with few exceptions in times of crisis, leading to the exhaust of traditional fuels. Changing the current processes of heat and electricity production cannot be done overnight and will take many years. For this reason, the development of new sources of clean and economically efficient energy is the no. 1 priority in the world. The modular solar solar-wind-hydro-wave-ocean stream-bio power plant with storage and reuse energy has an innovative character opposite to traditional procedures applied so far. The power plant can be achieved in different configurations depending on the types of renewable energy that exist in the area and the types of energy required (thermal and/or electric) with or without energy storage. Each module can work independently or connected with the central body which stores energy in the form of thermal energy and pressure energy and reuses it upon request or when needed. In a small size renewable power plant all processes are achieved with maximum efficiency related to random renewable energy collection, its conversion into electricity, energy storage and its use when needed. The modular renewable power plant with storage and reuse energy can generate, store and deliver thermal energy obtained directly from renewable energy. The quality of the thermal energy can be increased by raising its temperature using the thermal pump effect. Losses of thermal energy in the environment are recovered by air currents generated by the horn effect on the building faades. Air currents energy from the horn effect is transformed into electricity by cornice turbines mounted on the parapet of the micro-power plant. From an environmental point of view the new type of renewable power plants no longer have the disadvantages of classical thermal plants in that they are clean, do not consume large amounts of material and energy to achieve them, do not generate environmental hazards infection or accidents.
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The new type of renewable power plant is a way to the efficient exploitation of renewable wind and solar energy on an economical level and it is an important step in increasing the share of green energy use on an industrial scale. The possibility of storing renewable energy in the form of pressure energy and/or thermal energy and transform it into electricity when it is needed is a feature that enables the effective use of random renewable energy. Applying the new method may have an important contribution to the European directive "20/20/20", which involves the increase by 20% for the use of renewable in electricity production, 20% reduction in carbon dioxide releases, and 20% reduction in the intensity of energy use by 2020. [2] This paper presents a new type of modular power plant that uses renewable energy for the production and storage of electrical and thermal energy. [3, 4, 5, 6] The plant captures green energy that has a random character and stores it in the form of air pressured energy and heat. The plant can also work in a load curve adjustment system by power consumption in the night and day gaps and power production in the morning and evening peaks of the power system load curve. The power plant is designed so as to allow the collection, storage and supply of heat at the desired temperature. To determine the most effective ways to increase plant efficiency, storage of potential energy is made in several tanks of different capacities. These tanks are manufactured of reinforced concrete and steel. Some of these tanks can be used to store energy in the form of air under pressure and heat in multi-thermal tanks. The tanks are placed in a concrete and metal structure, on which are mounted: solar batteries, cornice and terrace wind turbines batteries and potential energy metal tanks. The power plant is made of several modules which can function independently or interconnected and which achieve: - The collection of two or more types of renewable energy (sun and wind or sun, waves and wind or sun, hydro and wind) using the same supporting structure for reducing investment on KW installed. - Renewable energy storage in tanks and for the long term (using as far as possible the same infrastructure ) to allow reuse it when necessary; - Utilization of the storage capability of renewable energy including for following the load curve; - Meeting the needs of heat and electricity for a relatively large community of persons, and for industrial needs along all the year. Current solutions for the collection of renewable energy within a specific site are inefficient (1 - 2 % of renewable energy in the region may collect), have large investments on KW installed and create difficulties in operation. The work presents several alternatives to build modules that allow efficient collection of renewable energy from an area. In some situations a number of modules connect between them to form a plant with posibilities to store renewable energy. According to the requirements of the users in some areas there can be built modules that work independently usually collecting three types of renewable energy using the same support structure. 2. SERB solar-wind-hydro-wave-ocean stream-bio power plant with storage and reuse energy to increase the efficiency of renewable energy (SERB RPP-01) The power plant can be achieved in several variants: solar-wind-hydro-plant; solar-windwave-plant; solar-wind-hydro-wave-ocean stream plant, etc. [7] The SERB RPP-01 power plant allows the storage of renewable energy as under pressure energy and/or heat and reuse it like heat or to converse it into electricity (using the same storage tank). The key particularity of efficient storage of the renewable energy as thermal energy in SERB RPP-01 plant is the recovery of a high percentage of the energy losses by chimney effect through the cornice wind turbines installed on the top of building plant and reuse it. The power plant can also be used for adjusting the load curve.
E nv nm en nt al Pr ec n. .I nd du us al Ri En vi ir ro on me ta lP ro ot te ct ti io on In st tr ri ia lR is sk k
Figure 2.1. SERB solar-wind-hydro-bio power plant with storage and reuse energy
Figure 2.2. SERB solar-wind-wave-bio power plant with storage and reuse energy with active cost protection
Figure 2.3. SERB solar-windwave-ocean stream-bio power plant with storage and reuse energy with active cost protection
Figure 2.4. Horizontal section and lateral view of a solarwind-hydro- wave-ocean stream -bio power plant
The advantages of using a SERB-RPP-01 power plant in adjusting the load curve are higher to the use of hydroelectric pumping power plant (CHEP) from the point of view of the initial investment, exploitation, environmental protection, for the following reasons: - They can be built anywhere due to the fact they are independent of the existence of a water source and a high capacity water accumulation basin; - They do not affect the ecological balance of the area; - The volume and time of construction works as well as the investment cost per MW installed are much lower than for a CHEP; - Fast Start up and close down of the SERB-RPP-01 (about 1 second) allows the instantaneous consumption or injection of power in electro-energetic system for adjusting the load curve; - Use in parallel of several functions which enable the efficient exploitation of renewable energy as well as adjusting the load curve of the electro-energetic system. - With an investment and a surface more lower than for a CHEP it is possible to obtain: greater total power installed in the electro-energetic system achieved by several SERB RPP-01; a relative uniform distribution of power in the electricity grid system which does not generate stability problems associated with a consumer or a high power injection in the electroenergetic system; no loss of energy due to the power transportation on the long distance;
If in the area are placed biodegradable materials the plant can contain a few digestion tanks that are located in the central module by the multi-thermal energy tanks. The digesters are located on the vertical axis in the optimal efficiency temperature area of biogas generating bacteria. Biogas production can be passed directly to the consumer or can be used to generate electricity or thermal energy in specialized equipment. The plant is constructed of a central module which allows the storage and reuse of energy and of several specialized modules, based on the potential of renewable energy in the location. SERB RPP-01 could be an important component for the efficient use of the renewable energy, all over the word, to achieve the aim of the Set - Plan and RES Directive 20/20/20 and for the implementation of the Smart cities concept. The central module is a relatively high building of reinforced concrete which contains hot water tanks and pressured air tanks. Solar energy is collected by panels mounted on the East, South and West facades of the building and on its terrace and transformed into electricity and heat which is used directly or stored in tanks. The wind energy of the natural air currents and air currents generated from the chimney effect is collected and transformed in electricity by terrace and cornice wind turbines. The chimney effect appears in the semi-opened channels formed between the walls of the plant (external plated by black terracotta/ tile) and the solar panels mounted on a support structure at a distance from the plant walls due to the temperature difference between the outside air and the temperature of the plants wall (this effect is maximized after sunset). The temperature in semi-opened channels is dependent on the intensity of the solar radiation and heat loss through the walls (thermally insulated) of the power plant. The renewable energy is stored in the form of thermal energy and pressure energy. The thermal energy is stored in hot water tanks whose temperature increases from bottom to top. Pressure energy is stored in under pressure air volumes which are found in independent tanks and/or in the upper side of the water tanks. The new type of solar-wind-hydro-bio plant is a simple installation that allows the efficient collection of solar, wind and hydro renewable energy and its conversion into electricity or heat, inclusively in areas with low solar-wind-wave-ocean stream energy potential that can be urban areas as well. The plant allows the storage of electrical energy in the form of under pressure energy and/or heat and converts it into electricity. The plant can also be used for adjusting the load curve. In a first version, the SERB-RPP-01 plant can be constructed on the shore of the flowing waters (rivers and streams) when specialized floating modules collect the kinetic energy of water currents as well as solar and wind power for the area concerned. These modules are connected with the central module built on the waterfront (bank) for energy transfer. In another variant, the power plant can be constructed on the sea or ocean shore when specialized floating modules collect wave energy from the off-shore as well as solar and wind energy for the area concerned by means of solar panels and wind terrace turbines mounted on specialized floating modules. These floating modules are connected with the plant constructed on the shore for energy transfer. In the event that there are water currents in the sea or ocean, the collection of their kinetic energy is made with specialized floating modules on which are mounted also wind terrace turbines and solar panels to collect energy from the area. An important feature of the new generation of solar-wind plants is that solar energy collection is done both directly through photovoltaic and thermal panels and indirectly by air currents due to the chimney effect generated by the temperature difference between the plants facades heated by solar radiation and the air temperature. Through this process, transformation of solar energy into electrical energy can be efficiently obtained also during cold periods because its effectiveness depends on the temperature difference between the facade surface and the air temperature. Also to be noted that heat losses from the plant which are higher during cold periods partially recover through the chimney effect. If a SERB-RPP-01 renewable power plant central module has a height of 41m and foundation dimensions of 20 x 28m with the overhead of a parallelepiped shape with horizontal section of 17 x 25m and 36m height:
the amount of heat accumulated in the tank can be between 500.000 to 700.000 kWh; the amount of energy accumulated inside pressure air volume can be between 800.000 to 900.000 kWh. According to necessity, the renewable power plant can produce: - a quantity of electricity between 250.000 to 350.000 kWh; - a quantity of thermal energy between 400.000 500.000KWh. Efficient energy storage plant ranges from 75-85% for heating and 25-35% for electricity.
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SERB RPP-01 can produce yearly electric power and heat from renewable sources for 6001000 people if the level of annual renewable energy recharge is 3. Energy losses are practically independent of ambient temperature variation due to their recovery through the chimney effect is high when ambient temperature is low which compensates for the losses increase with decreasing ambient temperature. 3. Modular floating solar-wind-hydro micro power plant to increase the efficiency of renewable energy (SERB RPP-02) The renewable energy of large flow running waters of the river has a high potential. Also solar and wind renewable energy in the vicinity of rivers is usually of maximal intensity generated by the geo-climate of the riverbeds. The renewable energy is manifested over a relatively long period of time at values with a good foreseeable intensity. At present the renewable energy potential related to river is not effectively exploited. The efficient exploitation of the 3 types of renewable energies (solar, wind and hydro) existing in the riverbeds area requires the development of new types of modular micro-plants that enable the efficient collection of these energies and their conversion into electricity using a single support structure. The collection of these energies must be done without affecting the initial ecosystem. The efficient exploitation of renewable energy can be made by means of modular floating solar-wind-hydro micro power plants SERB RPP-02.
Figure 3.1.Modular floating solar-hydro micro power plants
Figure 3.2.Modular floating solar-wind-hydro micro power plants
The plant collects the solar, wind and kinetic energy of the water flow. Achieving such a plant on a water course including those with low flow rate does not require the implementation of water storage dams that might affect the ecosystem both concerning the natural course of the river and the associated area. Modular floating solar-wind-hydro micro power plants can collect: The solar energy through solar panels mounted on the roof;
The wind energy using terrace wind turbines mounted on the ridge roof of floating hydro module; The kinetic energy of water currents by a cylindrical turbine and equipment that converts mechanical energy of rotation into electrical energy. Kinetic energy is converted into pressure energy by two floating crosspieces mounted in the front and rear sides of the plant which makes a hydraulic fall of a potential nearly double the potential for kinetic energy. Hydraulic fall is used to drive cylindrical turbine. Installation plant requires no hydro works construction and does not affect the flora and fauna of the watercourse. 4. SERB solutions for the efficient conversion of wave, solar and wind energy in electricity (SERB RPP-03) With respect to wave energy, we are working on the development of specialized equipment that can efficiently collect wave energy. This equipment can also collect solar and wind power for that area, in parallel with wave energy. Collecting the solar, wind and wave renewable energy using the same support structure and its transformation into electric energy is an efficient solution both in terms of low investment, surface and volume occupied by the equipment and because this energy practically covers a full range of a day. Depending on the waves energy and their type, equipment can be floating or fix. The equipment efficiency varies between 30% - 85% (function of the type of equipments). Equipment is made of high intensity polyethylene pipes, reinforced concrete, fiberglass, stainless steel and other materials resistant to sea/ocean water aggressiveness. Some equipments operate efficiently also with low amplitude waves, under 0.3 m. Equipment power is 0,1 up to 5 MW for waves of low and medium amplitude and 5 15MW for high amplitude waves. The investment for a wave turbine is under 50% of the investment for a wind turbines micro-farm of the same power. The cost of the electric power produced by SERB RPP-03 is comparable with the cost of electric power produced in thermal plants. SERB RPP-03 can achieve high active protection against erosion of the banks by taking over the waves energy. By using this equipment along the shores, in time there will be large sand deposits which will allow the formation of beaches. To collect solar energy on the lateral sides of the equipment and at the top solar panels are installed. For the collection of wind energy at the top the terrace wind turbines are installed.
Figure 4.1.SERB solutions for the efficient conversion of wave, solar and wind energy in electricity and active cost protection
5. SERB solutions for the efficient conversion of ocean stream energy, wind energy and solar energy in electricity (SERB RPP-04) Marine currents energy (global as well as those generated by tides) is very high. To collect kinetic energy of marine currents it has been conceived a new cylindrical modular floating turbine type. Depending on the water currents speed it is anchored only at the top for relatively low speeds and both top and bottom for relatively high speeds. Modular turbine diameter is small to get a rotation speed that does not require mechanical amplification systems. Blades are specially shaped to obtain maximum efficiency even at low speeds. Module rotor diameter mounted on the same shaft may differ with depth, to take into account the current speed variation with depth for obtaining maximum efficiency. To collect kinetic energy of water currents on a surface greater than the longitudinal section of the rotor at exterior of this is mounted a special housing that allows an energy concentration of water currents on active blades of the rotors. The housing is self oriented to the direction of water currents. The electrical part is classical one. If there are high or medium amplitude waves in the area were the SERB RPP-04 turbines are installed, the turbines can be connected to the SERB RPP-03 equipment.
Figure 5.1. The current marine turbines for small and medium speeds To collect solar energy on the lateral sides of the equipment and at the top solar batteries are installed. For the collection of wind energy at the top terrace wind turbines are installed. 6. SERB solutions for the efficient conversion of wind energy from urban area in electricity (SERB RPP-05) In wind energy field we developing a new generation of wind turbines (2nd generation) that do not exhibit exterior rotating parts, do not endanger the parts, do not generate annoying sounds, have a modular structure, high efficiency, they are not negatively influenced by the wind variation in height, require low investment and have an attractive architecture. [8] The new wind turbines can be achieved for the urban environment also (terrace, cornice and street wind turbines). The new urban wind turbines have no exterior rotating parts and have a modular structure made of removable components. The components of a module have sizes and weight that can be easily handled by 2 people. They can be manually lifted on the terrace of an existing building by 2 people. Installing these turbines on existing buildings is performed on the spatial light structures which don't affect the cover of the building. On the support structure of the wind turbines, panels may be mounted to collect solar energy.
6.1. SERB urban terrace wind power turbine Terrace wind-turbines are installed on the buildings terrace or buildings roof. tower-shaped and enclosed in a self-orienting carcass that facilitates collection, concentration and redirection of air currents; turbines can be grouped in micro-farms with a rigid position by ballasting and use of stiff cables to connect towers together and link the entire structure to a lightweight strong base; the terrace wind turbines are installed by the simple placement and ballasting on the terrace of the block without affecting the protection layers of a building.
Figure 6.1.1. Urban terrace wind power turbine module and micro- farm placed on top of the buildings The rotation housing (stator) of urban terrace wind turbines focuses and directs the air currents only on the active part of the rotor. 6.2. SERB urban cornice wind power turbine Cornice wind-turbines are installed at the perimeter of a buildings terrace or roof ridge. - cornice wind turbines can fully capture energy of ascending wind current generated by solar radiation (chimney effect) and super pressure on the facades as well as the energy of the horizontal air currents on the top sides of a building; - the losses of thermal energy on the inside of the building are recovered through the chimney effect by the cornice wind turbine; - has a special horizontal structure and deflectors that direct air currents and help generate vortices with suction effects; - simple installation procedure on a buildings cornice without affecting existing layers. - storage of the renewable energy can be made in pressure air tanks and this air can produce electrical energy by discharging in the cornice wind turbine. - a string of modules can be connected (micro-farm) to electric generators placed at either one or both ends.
Figure 6.2.1. Cornice module and string of cornice modules installed on building
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6.3. SERB urban street wind power turbine Circulation of vehicles on highways and trains on railways and subway generates high speed air currents. If the vehicle flow is high air currents can be used to produce power with street turbines mounted on the edge of the transport corridors. In certain areas these turbines can also use natural air currents generated by the differential heating of the earth's crust. On the support structure of the street wind turbines, panels can be mounted to collect solar energy. Energy obtained from these turbines can be used to supply services necessary for the operation of the transport artery (highways and trains on railways and subway) or it can be delivered to a power system. - the movement of speed vehicles (cars, trucks, trains, subways) generates air currents (wind locally) to a distance depending on vehicle size and shape. - if in the middle of the street (highways) and on the sides (in some areas) street wind turbines are assembled, these can capture up to 45% of the energy of air currents generated by the movement of vehicles. - the street wind turbine can also collect natural wind energy. - micro-farm wind turbines can be manufactured so that they also serve as sound-absorbing panels making a significant reduction of noise generated by moving vehicles (the solution has maximum efficiency for railway). - micro-farm wind turbines on the street can ensure safety by physical separation of the traffic ways (replacing the current separation items) and role of protecting from the headlights of cars that run in reverse direction.
Figure 6.3.1. Urban street wind power turbines modules and micro-farm placed on the central and side strip of a highway 7. SERB on-shore wind power turbine micro-farm for the efficient conversion of wind energy in electricity (SERB RPP-07) In wind energy field we developing a new generation of wind turbines (2nd generation) that do not exhibit exterior rotating parts, do not endanger the parts, do not generate annoying sounds, have a modular structure, high efficiency, they are not negatively influenced by the wind variation in height, require low investment and have an attractive architecture. The new wind turbines can be achieved and for the on-shore. This project refers to the development of a new type of on-shore wind turbines. On-shore wind turbines are mounted on fixed platforms or mobile platforms in rotation which can rotate in the direction of propagation of wind. The new wind turbines have no exterior rotating parts and have a fix position on the mobile platform. This new concept allows the installation of solar panels on the wind turbines and on the mobile platform, which leads to the efficient collection of renewable energy (solar and wind) in the site.
The total power of the new turbines installed on a platform equal in size to that used for a classical 2 MW wind turbine is of 50-60 MW. Taking into account that this new concept allows the collection of solar energy in the site, the proposed solution has higher efficiency than the classical solutions. Electricity generated by a on shore SERB wind turbines micro-farm can produce up to 100 times more energy than a on-shore classical wind turbine micro-farm using an equivalent area.
Figure 7.1. Grid layout of turbine towers in on-shore. Alternative 2. Mobile platform. 8. SERB off-shore wind power micro-farm for the efficient conversion of wind energy in electricity (SERB RPP-06) In wind energy field we developing a new generation of wind turbines (2nd generation) that do not exhibit exterior rotating parts, do not endanger the parts, do not generate annoying sounds, have a modular structure, high efficiency, they are not negatively influenced by the wind variation in height, require low investment and have an attractive architecture. The new wind turbines can be achieved and for the off-shore. This project refers to the development of a new type of off - shore wind turbines. Off - shore wind turbines are mounted on floating platforms of high stability which can rotate (self orienting) by the direction of propagation of the wind. The new wind turbines have no exterior rotating parts and have a fix position on the floating platform. This new concept allows the installation of solar panels on the wind turbines and on the platform, which leads to the efficient collection of renewable energy (solar and wind) in the site. The total power of the new turbines installed on a platform equal in size to that used for a classical 2 MW wind turbine is of 50-60 MW. Taking into account that this new concept allows and the collection of solar energy in the site, the proposed solution has higher efficiency than the classical solutions. A new off-shore wind turbine farm can produce up to 100 times more electric energy than a classical turbine wind farm using an equivalent area.
Figure 8.1. Off-shore wind turbine micro-farm installed on self orienting floating platform.
9. SERB solutions for the efficient conversion of tidal energy, wind energy and solar energy in electricity (SERB RPP-08) The tidal wave turbine is structurally and functionally similar to the new wind turbine (SERB RPP-03-W3), but it is much larger in rooms dimensions and has a fixed position. In the tidal wave turbine, a much larger volume of water enters and exits each chamber, but has a smaller dynamic flow because filling and emptying the chamber is done in 6 hours and 12 minutes. Tidal waves turbines must be located near shores where tide amplitude is maximal and they have a fixed position. Tidal wave turbines may also collect wind wave energy that overlaps the tidal waves as both act the rotor blades in the same direction so that the effects of the two waves (wind and tidal waves) overlap and amplify one another. Tidal wave turbines may be built out of concrete, steel or composite materials, and using the new type of highly resistant, advanced textiles.
Figure 9.1. SERB Tidal wave turbine SERB RPP-08 can be successfully used for aquaculture, tourism, etc. With this respect, the inlet and outlet rooms can have a compartment structure at the top in order to achieve constructions specific to the respective activity. To collect solar energy on the compartment structure the solar panels are installed. For the collection of wind energy on the compartment structure the terrace wind turbines are installed. 10. CONCLUSIONS The new type of renewable power plant with energy storage and reuse allows the efficient collection of solar and wind renewable energy and its conversion into electrical and thermal energy, inclusively in areas with low energy potential that can be urban areas as well. The renewable plant allows the storage of electricity in the form of under pressure energy and/or heat and converts it into electricity. The plant can also be used for adjusting the load curve. An important feature of the new generation of renewable power plant is that solar energy collection is done both directly through photovoltaic and thermal panels and indirectly by air currents due to the chimney effect generated by the temperature difference between the building plants facades heated by solar radiation and the air temperature. Through this process, transformation of solar energy into electrical energy can be efficiently obtained also during cold periods because its effectiveness depends on the temperature difference between the building facade surface and the air temperature. Also to be noted that heat losses from the micro-plant building which are higher during cold periods partially recover through the chimney effect. The collection of renewable energy from one area is made by means of modules which may collect simultaneously or alternately three types of renewable energy: sun-wind-hydro or sun-windwaves or sun-wind-marine currents. The plant may contain high efficiency modules for generating
biogas, taking into consideration the possibility of maintaining the optimal temperature for the digestion area throughout the year. The new solutions for the efficient collection of renewable energy and its conversion into electricity and/or heat presented have a great development potential for the following reasons: - the renewable power plant SERB-RPP-01 is easily to construct, including in the urban areas where the need for electricity and heat is higher; - it is effective also in areas with low temperature; - it is a plausible alternative to achieve in power independent areas (residential areas) because they allow the collection of random renewable energy and its use when needed; - it can produce electricity and heat in large quantities over long periods (summer till winter); - it can take over large variations of power specific to small communities and may act as an installation by adjusting the load curve with high efficiency; - it requires small investments, without affecting the environment; - it can be a solution for efficiently adjusting the load curve; - the building of renewable power plants in a site requires relatively small consumption of materials and energy and could be done in a short time without the need of special high power machines. The wind turbines for collection wind energy installed in the renewable power have a great development potential for the following reasons: - it remove nearly all the disadvantages of classical urban wind turbines; - they have a modular structure with components whose dimensions and light weight allow easy handling without specialized equipment and can be fitted including on existing buildings; - cornice and terrace wind turbines efficiently collect the energy of natural airflow (including slow speed ones) as well as the artificial air flow - the chimney effect (another way to collect and store solar power the chimney effect depends on the temperature difference between the facade of the building and surrounding environment and is maximal after sunset, when the electricity demand is maximum); - street wind turbines efficiently collect the energy of currents generated by motor vehicles movement (trains, trams, buses, etc.) as well as natural air currents energy; - they do not have exterior rotating parts, are silent and do not present any danger to birds; - they are easily accomplished, fitted and operated; - they are also efficient in low temperature areas. - off-shore wind turbine towers are mounted on circular, floating, self-rotating platforms that can move in a circular motion; - off-shore wind turbines are vertical axis turbines, the turbine collects the direct and as well as indirect (through suction) wind energy from a large rectangular surface; - off-shore turbines and modular floating platforms have a modular structure with components whose size and weight allow their transportation by traditional means of transport; - installing off-shore turbines and modular floating platforms can be achieved with conventional machines; - they efficiently collect the energy of natural airflow as a micro-farm module is orienting itself on the direction of airflow, which ensures the efficient collection of its energy (this allows the establishment of a space structure of wind turbines that are independent of the direction of propagation of the wind); - variable speed of airflow by height does not influence negatively the efficiency of vertical turbines because there has been a change in the turbine impeller (rotor) diameter at a certain height proportional to the speed of air currents at a certain height; - the platforms on which wind turbines are mounted have a high stability due to both their pyramid shape oriented downwards, their ballasting to the bottom and because between the components of the platform modules have a water layer which generates friction forces to any deviations from the vertically equilibrium position;
are easily accomplished, mounted and operated. Taking into account the rapid evolution of climate change occurring lately, the existing technical solutions currently producing energy for life and necessary activities, the forecast regarding classical energy resources depletion, the solution to this critical situation is the efficient exploitation of renewable energy resources, storing and reusing it. The solutions proposed in this paper are an alternative which if implemented would allow solving this problem in very short time.
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For further information please contact Mr. SERBAN VIOREL, tel. +40722615672 or +40214046006, fax +40214574431, e-mail: office.sigmass@gmail.com; serbanv@router.citon.ro; viorelserban49@yahoo.com
REFERENCES 1. Sisteme de conversie a energiilor regenerabile - Boston, V. Dulgheru, I. Sobor, V. Boston, A. Sochireanu, , Editura Tehnica- INFO Chisinau, 2007. 2. Europes onshore and offshore wind energy potential An assessment of environmental and economic constraints European Environment Agency - 2009. 3. Installation and Procedure for Entrapping Wind Kinetic Energy and Transforming it Into Mechanical Rotation, Respectively Electric, Energy - Invention patent application no. A/00516 Bucharest OSIM 10.06.2010, Authors: Serban Viorel; Serban Laura Elena; Postolache Viorela Maria; Pordea Viorel. 4. Installation and Procedure for Generation of Air Flow to Act on a Turbine in Order to Produce Electricity - Invention patent application no. A/00473 Bucharest OSIM 16.05.2011 Authors: Serban Viorel; Serban Laura Elena; Postolache Viorela Maria; Pordea Viorel. 5. High Power Reactive Wind Turbines - Wec Regional Energy Forum FOREN 2010 Neptun, 13-17 June 2010. 6. Installation and Procedure to Build a High Capacity Floating Platform - Invention patent application no. A/01131 Bucharest OSIM 18.11.2010, Authors: Serban Viorel; Serban Laura Elena; Postolache Viorela Maria; Pordea Viorel. 7. Solar-Wind Micro Power Plant With Possibilities to Store Power and to Follow Up the Load Curve - WEC CENTRAL & EASTERN EUROPE ENERGY FORUM FOREN 2012, Neptun - Olimp, Romania, 17-21 June 2012 - Viorel Serban, Adrian Panait, Madalina Angela Zamfir, George Alexandru Ciocan, Marian Androne, Laura Elena Serban, Liviu Dan Postolache, Viorela Maria Postolache. 8. New Solutions for Converting Wind Energy Into Electricity - WEC CENTRAL & EASTERN EUROPE ENERGY FORUM FOREN 2012, Neptun - Olimp, Romania, 17-21 June 2012 - Viorel Serban, Adrian Panait, Madalina Angela Zamfir, George Alexandru Ciocan, Marian Androne, Laura Elena Serban, Liviu Dan Postolache, Viorela Maria Postolache.
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EVALUATING MACROMINERALS CONTENT OF BONE MEAL POWDER Claudia Sandru, Felicia Bucura, Marius Constantinescu
National R&D Institute for Cryogenics and Isotopic Technologies ICIT Rm. Valcea Code 240050 - Rm. Valcea, Uzinei 4, CP 7 Raureni, Valcea, Romania, e-mail: sandru@icsi.ro
ABSTRACT Fertilizers are largely made from the waste products of slaughter houses, such as blood, bits of waste meat and other refuse, bones, hoofs, horns, and hair. Bone meal is used as a phosphate fertilizer type and is available in two types: raw and steamed. This organic residue contains substantial amounts of organic matter and nutritive elements such as N, P and Ca. It is more brittle and can be ground into a powder form. Because the pace of releasing the nutrients is rather slow, bone meal powder makes an excellent natural time-release fertilizer classically employed to prepare the soil for planting. The use of MBM as a fertiliser is comparable to the effect of soft rock phosphates and this, on normal agricultural soils, is hardly available for plants. The present study is intended to provide data on the macromineral composition of two bone meal samples that will aid in the development of the applications described above. Total concentrations of macrominerals in the bone meal were analyzed according the microwave aqua regia digestion, using Mars 5 Microwave System. Major minerals leves in bone meal samples were analyzed by flame atomic absorption spectroscopy (Ca, Mg, Na, K, Mn, Zn, Fe) and UV-VIS absorption spectroscopy (P), at the levels mg/kg. Keywords: fertilizer, bone meal, macrominerals
THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE INDUSTRIAL AREA OF RM. VALCEA Mihaela Iordache1,2, Ioan Viorel Branzoi2, Ioan Iordache3, Nicoleta Georgeta Dobre2, Georgeta Totea2
1
National Research and Development Institute for Industrial Ecology Ramnicu Valcea Subsidiary, 1 Uzinei Rm Valcea,240050, phone: 0040 250 732 744, fax: 0040 250 732 746, E-mail: iordache.ioan@icsi.ro 2 Polytehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7, Polizu Street, Sector1, Bucharest, 011061, Romania; 3National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania
ABSTRACT
This study aims to establish the environmental impact on the degree of accumulation of priority hazardous substances soil, water and sediment in the industrial platform Ramnicu Valcea. Water and sediment samples were collected in two campaigns, in May and August 2011, and soil samples was collected in May and October 2011. Nickel, copper, cadmium, 1,2 dichloroethane, trichlorethylene, 1,2,4 trichlorobenzene and perchlorethylene were analyzed from water, soil and sediment. Concentrations of priority hazardous substances in water, upstream and downstream of the industrial area showed lower limits than those indicated in the National Legislation. The results show that heavy metals in sediments collected from the Olt River, (Priza Olt and Cremenari), generally fall within the limits imposed in National Legislation. It also observed that in all three points, 1,2 dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1,2,4 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation 141
E nv nm en nt al Pr ec n. .I nd du us al Ri En vi ir ro on me ta lP ro ot te ct ti io on In st tr ri ia lR is sk k trichlorobenzene taking values below the detection method. From soil samples analyzed is found insignificant soil pollution with heavy metals (nickel, copper, cadmium) and the organochlorine substances (1,2 dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1, 2,4 trichlorobenzene). Keywords: organochlorine substances, heavy metals, surface water, sediments, Olt River
EDUCATION FOR SUSTAINABLE DEVELOPMENT Oana Ramona Grigoriu, Ionela Halcu, Giorgian Neculoiu, Virginia Cristiana Sndulescu, Alexandru Viorel Marinescu, Mariana Marinescu
Technical University of Civil Engineering Bucharest, Faculty of Hydrotechnics, Automatics and Applied Informatics Collective, Lacul Tei Boulevard, No. 124, Sector 2, Bucharest, Phone number: +4 021-242.12.08, Fax: +4 021-242.07.81 E-mail: alexandru.viorel.marinescu@gmail.com, mmarinescu54@gmail.com, s_virg@yahoo.com, halcuionela@yahoo.com, oana.grigoriu@yahoo.com, neculoiu_giorgian@yahoo.com
ABSTRACT
Sustainable development is best defined in The Report of the Brundtland Commission, Our Common Future as the development that "meets the needs of the present without compromising the ability of future generations to meet their own needs. Sustainable development is found at the crossroads of environment, economics and society. As a result there is a need for a knowledge base from the natural-sciences, social-sciences and humanities to understand the principles of sustainable development, how can it be implemented, the values it involves and the ramifications of their implementations. Education, in addition to being a human right is a mandatory requirement for achieving sustainable development. Education for sustainable development strengthens the capacity of individual, communities, organizations and countries to make judgments and choices in favor of sustainable development. It can provide critical reflection and greater awareness and empowerment so that new visions and concepts can be explored and new methods and tools can be developed. The aim of this paper is to show some possibilities of integrating education for sustainable development in universities, especially in the system engineering field and the benefits than can arise from doing this.
1. WHAT IS SUSTAINABLE DEVELOPMENT? At a global level, the concern about sustainable development began in 1972 at a ONU Conference held in Stockholm. The term eco-development was used then. The term sustainable development started being used in the early eighties and was officially launched in 1987 in the Brundtland Report, Our Common Future. The term was defined in the same report as the development that "meets the needs of the present without compromising the ability of future generations to meet their own needs. [1] The main concern about sustainable development suggests that meeting the needs of the future depends on how well we balance social, economic, environmental objectives and present needs when making decisions. Among others, conserving and enhancing resource base and reorienting technology were two of the critical objectives stated in the Brundtland Report [1]. The energy consumption chart by sectors (in the USA, 2009, according to Energy Information Administration) shows that the energy consumption is divided as follows:
- 32% - the industrial sector; - 29% - for transportation; - 21% - for the residential sector. Here, the consumption is divided like this: space heating 60%, hot water 24%, lighting 3%, cold appliances 3%, consumer electronics 3%, cooking 3%, wet appliances 2%, miscellaneous 2%; - 18% for the commercial sector. Human impact on the environment is or is becoming a priority concern for governments and businesses world-wide. 2. EDUCATION AND SUSTAINABLE DEVELOPMENT Education for sustainable development should begin for children at early ages. Environmental education of children is imperative in order for the next generation to develop an earth-healthy lifestyle. There are already programs, worldwide, that promote living a sustainable life to children, but most important, children should be taught by example, so that they will perceive sustainability as a moral duty that we all have that leads to a good quality of life. Children should be taught to make conscious decisions about ones actions impacts on the community and the environment, to learn to reduce their consumptions, reuse what they can, and also recycle what they can, so they will overcome the consumerism behavior that present generation has. This can be done all the way from kindergarten to high school. At early ages they should learn about the environment factors, learn to respect nature and as they grow up to learn about the social and economic impacts their way of living can have. The main purpose of teaching sustainability is to make everybody conscious about their moral duty to preserve the environment and to see the linkage between their actions and their quality of life. There are a few things that any person could do for living a sustainable life, like: - turning down the thermostat and the water heater; - weather seal your homes windows doors, ducts, plumbing, improve insulation of walls; - turn off and unplug electronic equipment and lights when not in use; - use more efficient, less polluting vehicles; commute by bus, bike, car sharing or walking; go car-free one day a week; - recycle. 3. WHAT IS SUSTAINABLE ENGINEERING? We live in an engineered world and every aspect of the human life is underpinned by at least one engineering ramification. Sustainable engineers can interfere with all the major fields like: water supply, housing and shelter, sanitation and waste management, energy development, transportation, development of natural resources, cleaning up polluted waste sites, food production, planning projects to reduce environmental and social impacts, restoring natural environments such as forests, lakes and streams, improving industrial processes to eliminate waste and reduce consumption, recommending the appropriate and innovative use of technology [7]. Because of the fact that engineering has such an impact on human living and on the planet, we need to provide engineering students with the knowledge and skills to help industry and commerce reduce their negative environmental impacts and support the objectives of sustainable development, radical thinking to develop new engineering thinking and solutions in respect of product design, energy and materials efficiency, waste minimization, product recovery and recycling. This means we need to teach sustainable engineering. By comparing traditional engineering with sustainable engineering the following major differences between them can be seen [6]:
traditional engineering considers the object to be designed, whereas sustainable engineering considers the whole system in which the system will be used; traditional engineering focuses most on the technical issues, whereas sustainable engineering integrates technical and non-technical issues; traditional engineering solves the problem thinking about the present and the immediate future, whereas sustainable engineering is keen to solve the problem for the indefinite future; traditional engineering considers the local context (the users), whereas sustainable engineering considers the global context. 4. EDUCATION FOR SUSTAINABLE ENGINEERING Sustainable engineering comprises environmental technology which can be defined as a technology that reduces human and ecological risks (better for us and nature, during production), enhances cost effectiveness, improves process efficiency (more with less materials and less energy), creates products and processes that are environmentally beneficial or neutral (better for us and for nature, during use and at disposal). There is one clarification that needs to be made: there is education for sustainable development for all kinds of engineering fields like System Engineering, Civil Engineering and so on and education for Sustainable Development Engineering. To make things more clear, we will give an example. In the Technical University of Civil Engineering of Bucharest, Faculty of Hydrotechnics there is a Bachelor Degree program called Environment Engineering, in the field called the same way, Environment Engineering and the Master Degree Program called Sustainable Development. For the graduates of these programs, Sustainable Development is their major. The Department of System Engineering, Automation and Applied Informatics Specialization, Faculty of Hydrotechnics of the Technical University of Civil Engineering of Bucharest prepares students that can interfere in their future work as engineers with all of the major fields presented in Chapter III of this paper (water supply, housing and shelter, ). That is why they need to be aware of the impact their work will have on the environment and that is way they need to learn about the principles of sustainable development and how to apply them in their work as engineers. In the following part of the paper, we will be presenting what we think is necessary for the students in different types of engineering, but not the ones that major in Sustainable Development Engineering. When it comes to talking about teaching sustainable engineering, there are two main aspects that need to be considered [6]: 1. What are the main principles of sustainable engineering and how can they be applied to solve technical problems? 2. How can sustainable engineering be taught to the next generation of engineers? Integrating the study into existing courses or by creating new courses or even new curricula? During product design, an engineer that considers sustainable development in his work should study the implications of his work not only in the immediate future, but also in an indefinite future, to think innovative and creative, to include recent research and alternative solutions. The main purposes of sustainable engineering that must be considered are to maintain the integrity of global and local ecological systems, to ensure that the cost of resource depletion is included, to minimize the use of non-renewable resources and maximize the use of renewable resources and minimize waste production, preferably as near to the source as possible. A question that arises when trying to teach sustainable engineering is whether to create new subjects or embed the study in existing subjects. Considering the fact that the engineering curriculum is already completely full, leaving little or no room for adding new subjects, the most appropriate solution seems to be to incorporate sustainability case studies in existing subjects, so that the student can become familiar to new and alternative solutions for traditional projects. It is recommended to add a new discipline that presents the basic concepts of sustainable engineering
and the available tools that might help engineers design in a sustainable way. However, inserting a new discipline in an engineering curriculum that is already full of needed fundamental subjects might be a difficult task. In the relevant subjects that already exist in the engineering curricula like Computer technologies (e.g., CAD, CAE, CAM), High Precision technologies (e.g. Computer Numerical Control), Information technologies, Advanced robotics and other intelligent production systems, Automation (e.g. for green buildings Building Management Systems), Control systems to monitor processes (e.g. SCADA, Distributed Control Systems), New industrial platform technologies, modules comprising relevant sustainability case studies can and should be inserted. All these disciplines should be taught in a manner that gives the students an understanding of the principles and practices of sustainable development, enables students to select and utilize appropriate design methods and techniques to improve the quality and management of product innovation, gives the students an understanding of what product lifecycle means, use product lifecycle management tools, provides an understanding of the tools and techniques available to facilitate sustainable product design and provide knowledge of the product design processes that can reduce environmental impacts and promote sustainable practices. [4], [5] There are sustainability tools that come to help engineers in most of the existing fields and, probably, more are to be developed. For example, in civil engineering the following tools are available: Building Research Establishment Environmental Assessment Method, Comprehensive Assessment System for Built Environment Efficiency, Sustainable Project Appraisal Routine SPeAR), in manufacturing there is CCalc a carbon footprinting tool that enables easy estimation of the life cycle greenhouse gas emissions, IChemE a set of indicators that can be used to measure the sustainability performance of an operating unit in the process industries. Teaching sustainable engineering is still a developing field, methods and tools are not fully defined. Nevertheless, we have to continue our efforts until designing in a way that integrates social, environmental and economic considerations will be the only way to design. 5. CONCLUSIONS In order to reach sustainable development, we all need to be conscious about the social, economic and environmental impacts our actions have. For that, there is a need to teach sustainability to students all ages so that all members of the society gain the moral values needed to live a sustainable life. Engineers have the moral obligation to consider all the aspects of the impact their work have, not only the technological aspects. As a means for that sustainable engineering should be taught in technical universities, so that the next generation of engineers will have the necessary knowledge. We need to be aware of the necessity to build an engineering education system that produces engineers capable of rational, innovative and ethical design that consider all the aspects of an engineering project with all the implication at a global level and in an indefinite future, that doesnt just satisfy the present needs. Considering the fact that principles of and tools for sustainable engineering are not fully developed, this will probably happen slowly, but, nevertheless, efforts must be made towards the right direction. As a synthesis, we have made the poster presentation attached, which contains all the relevant information of the paper in a structured way. REFERENCES 1. World Commission on Environment and Development, Our Common Future, Oxford University Press, 1987 2. Gerry Te Kapa Coates, Sustainability & Engineering Practices Overview, Ipenz Publication, 2003
3. David Allen, David Shonnard, Sustainable Engineering: Concepts, Design and Case Studies, Prentice Hall, 2011 4. Braden R. Allenby, David T. Allen, Cliff I. Davidson, Teaching Sustainable Engineering, Journal of Industrial Ecology, Volume 11, Number 1, 2007 5. Slobodan Perdan, Adisa Azapagic, Roland Clift, "Teaching sustainable development to engineering students", International Journal of Sustainability in Higher Education, Vol. 1 Iss: 3, 2000, pp. 267 - 279 6. Benoit Cushman-Roisin, Sustainable Engineering available at http://www.ce.utexas. edu/prof/hart/333T/documents/SustainableEngineering.pdf 7. Wikipedia, The Free Encyclopedia, Sustainable Engineering, available at http://en. wikipedia.org/wiki/Sustainable_engineering
LOG-NORMAL DISTRIBUTION OF THE SUSPENDED PARTICULATE MATTER (PM10) APPLICATION IN CRAIOVA, ROMANIA (2012) Liana Simona Sbirna1, Teclu Codresi2, Anisoara Oubraham3*, Sebastian Sbirna2
1
University of Craiova, Faculty of Exact Sciences, Chemistry Department, 107I Calea Bucuresti. Craiova, (+40)251.597048; 2Saint Stephen Ecological School, 15Constantin Brancusi Street, Craiova, (+40)251.420534; 3National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, 4 Uzinei Street, Ramnicu Valcea,(+40)745.61398, (e-mail: anisoara@icsi.ro)
ABSTRACT
The present paper reports the results of a statistical analysis of particulate matter (PM10). The concentration values were gathered from one of the five automatic stations situated in Dolj County continuously monitoring air quality during a period of one years (between July 1st, 2011 and June 30th, 2012). A log-normal distribution is proved to best fit the experimental curve. The distribution is also related to the wind velocity, showing that in most cases a low value of the wind speed leads to a high value of the pollutants concentration. Keywords: monitoring air quality, PM10, statistical distribution, wind velocity, Craiova
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MATHEMATICAL MODELS USED IN DESCRIBING AIR POLLUTANTS DISPERSION APPLICATION IN CRAIOVA, ROMANIA (2012) Teclu Codresi1, Sebastian Sbirna1, Liana Simona Sbirna2*, Anisoara Oubraham3
1
Saint Stephen Ecological School, 15 Constantin Brancusi Street, Craiova, (+40)251.420534; 2University of Craiova, Faculty of Exact Sciences, Chemistry Department, 107I Calea Bucuresti. Craiova, (+40)251.597048; 3National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, 4 Uzinei Street, Ramnicu Valcea, (+40)745.61398, (e-mail: anisoara@icsi.ro);
ABSTRACT In this paper, a log-normal model and a normal model are applied, one at the time, to predict the impact of an atmospheric release of air pollutant, the results being than compared with the real data recorded for two air pollutants, namely PM10 and SO2, during half a year (between October 2011 and Mars 2012). The study shows that the first one is better described by the log-normal model, whereas the second is suitable to be treated in the normal one. Keywords: air pollutants, PM10, SO2, log-normal distribution, normal distribution, Craiova
VARIATION OF THE OLT RIVER QUALITY INTO THE INDUSTRIAL COMPLEX AREA OF RAMNICU VALCEA Iordache Mihaela1,2 , Branzoi Ioan Viorel2, Iordache Ioan2, 3, Popescu Luisa Roxana1,2, Maria Taralunga1
National Research and Development Institute for Industrial Ecology, Ramnicu Valcea Subsidiary, 1 Uzinei, Rm, Valcea,240050, Romania; 2Polytehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7, Polizu Street, Sector1, Bucharest, 011061, Romania; 3National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT, Rm. Valcea, 4 Uzinei St.,240050, Romania; e-mail: iordache.ioan@icsi.ro, phone:0040 250 736979, fax:0040 250 732746
1
ABSTRACT
The aim of this study was to present evolution of the Olt River water quality in the Ramnicu Valcea industrial aria in the last four years (2008-2011). This study was realized in order to determine the degree of the water pollution in the industrial platform Ramnicu Valcea, Romania. The main factors which affect the Olt River water quality in the Ramnicu Valcea are: industrial activities, the hydro-electric plant programs, the quantity of precipitation and the other pollutant accidents. According with our results, in the last four years there was no heavy metals pollution: mercury, nickel, chromium and cobalt, in all three sections of this study. In all section, -HCH isomer, was situated under limit of 0.02 g/l, 1,2 dichloromethane was under limit of 10,0 g/l imposed by National Legislation, the other organochlorine chemicals (hexachlorobenzene and 1,2,4 trichlorobenzene) taking values below the detection method. Keywords: heavy metals, organochlorine substances, surface water, inorganic compounds
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DETAILED CHARACTERIZATION AND PROFILES OF AMBIENT ATMOSPHERE MONITORING USING AUTOMATIC TECHNIQUES FROM IN SITU COLLECTED SAMPLES Diana Florescu, Roxana Ionete, Felicia Bucura, Marius Constantinescu, Gili Saros
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no.4; P.O. Box 7 Rureni, 240050, Rm.Vlcea, Romania, e-mail: diana.florescu@icsi.ro
ABSTRACT
In general, air quality monitoring has an essential role in the environment monitoring system. The atmosphere is a proper medium for pollutants to spread in the environment reason for an on-site monitoring of an industrial area in the southern-east of Romania, near Calarasi. This monitoring starts with May 2009 and continues with seasonal collecting data for year 2009 and 2010. For on-site analysis portable analyzers, part from a complex system of ICIT Rm. Valcea mobile laboratory, were used. These automatic analyzers can monitored a wide range of pollutants as CO2, CO, NO, NO2, SO2, PM10, O3, CH4, THC, besides meteorological parameters like wind speed, wind direction, temperature and humidity. In addition to these three conventional parameters, we also monitories special parameters like NH3, H2S. The carbon monoxide, sulfur dioxide, nitrogen dioxide, ozone and particulate matter in the outdoor atmosphere concentrations were measured and recorded according with the Romanian legislation no. 592/25.05.2002, and no 462/01.07.1993. With the exception of particulate matter concentrations, the results have shown a quite low level of pollution in the studied area. Keywords: environment, in situ monitoring, ambient air, health risk.
METHODS USED TO ESTIMATE THE GREENHOUSE GAS EMISSION POTENTIAL FROM SOLID WASTE DISPOSAL E. David1, N. Aldea2, S. Preda3, A. Armeanu1, C. Sandru1, F. Bucura1, M. Constantinescu1, D. Mocanu1
National Research Institute of Cryogenics & Isotope Technologies, Street Uzinei no.4; O.P Rureni; P.O.Box 7, 240050 Rm.Vlcea, Romania, david@icsi.ro; 2National Research Institute for Isotopic and Molecular Technologies,Str. Donath, No. 65-103; 400293, Cluj-Napoca, Romania; 3Research Station for Fruit Growing Valcea,Calea lui Traian, no. 464, 240263, Rm.Valcea, Romania, predasilvia@yahoo.com
1
ABSTRACT
Environmental policy in waste management leads to increasing interest in developing methods for waste disposal with minimum emissions of greenhouse gases and minimum environmental impacts.Open dumping, landfilling and modern waste combustors (MWCs) are the prevalent solid waste disposal practices in many countries. Surveys on the disposal sites revealed the presence of numerous landfills ,open dumps and waste combustors. Greenhouse gas emission potential at these sites can be estimated by different methods. The purpose of this paper is to establish a more robust technique for determining the potential of gas emissions from municipal solid waste and to use those results in a life cycle assessments that determines the GHG impacts of modern MWCs and landfills. Methane emission potential at these sites was estimated by three methods. Results of the Intergovernmental Panel on Climate Change (IPCC) method, Landfill Gas Emission model (LandGEM), and closed flux chamber technique were compared. For the facilities analyzed , the methane emission potential of 18.94 Gg/yr using the IPCC method was higher than the estimations of the 148 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
E nv nm en nt al an nd dL eQ ua al En vi ir ro on me ta la Li if fe Qu li it ty y LandGEM and closed flux chamber method of 5.95 Gg/yr and 5.33 Gg/yr, respectively. From the point of view of nitrous oxide (N2O) emissions, waste incineration and waste co-combustion are acceptable methods of waste disposal. Two factors are important for attaining low NOx emissions from waste combustion , particularly for waste with higher nitrogen content (e.g. sewage sludge, leather, etc.): temperature of incineration over 900OC and using of modern incinerators with selective catalytic reduction (SCR) or selective noncatalytic reduction (SNCR) deNOx facilities. The catalysts used in SCR based facilities are among others Fe-zeolite and V2O2.This catalysts have high N2O decomposition (and SCR) activity with good hydrothermal stability.This data are essential to assess the potential need of abatement measures to limit N2O emissions in future operation of waste incineration plants. Keywords: MSW, CH4 , NOx emission, landfill, open dump, incineration, selective catalytic reduction
1. Arena U, Mastellone M.L., Perugini F.,(2003)The environmental performance of alternative solid waste management options a life cycle assessment study. Chemical Engineering Journal, Vol. 96,207-222. 2. Solano, E., Ranjithan, S., Barlaz, M. A., and Brill, E. D.,(2002) Lifecycle-based solid waste management I: Model development., J. Environ.Eng., 10, 981992 3. Intergovernmental Panel on Climate Change (IPCC) (2001),Climate Change 2001: The Science of Basis, Technical Summary; Cambridge University: New York; 4. Intergovernmental Panel on Climate Change (IPCC).(1996) IPCC Guideline for National Green House Gas Inventories Workbook [Online]; available at http://www.ipcc-nggip.iges.or.jp/ public/gl/invs5.htm (accessed from June 2005) 5. Users Manual: Landfill gas emission model: Version 2.1(1998), U.S. Environmental Protection Agency; Office of Research and Development: Washington D.C. 6. Reinhart, D.R.; Cooper, D.C.; Walker, B.(1992) Flux chamber design and operation for the measurement of municipal solid waste landfill gas; J. Air & Waste Manage. Assoc., 42,10671070
STUDIES ON THE IMPORTANT POLLUANTS OF WASTEWATER FROM TEXTILE INDUSTRY Claudia Sandru, Elena David, Felicia Bucura, Marius Constantinescu
National Institute for Research and Development for Cryogenics and Isotopic Technologies ICIT Rm. Valcea, Uzinei Str. 4, RO-240050, Rm. Valcea, Romania, e-mail: claudia.sandru@icsi.ro; elena.david@icsi.ro; felicia.bucura@icsi.ro; marius.constantinescu@icsi.ro
ABSTRACT
The specific water intake for the textile industry varies depending on the type of processes used and water efficiency. Dye house effluents are complex, containing a wide and varied range of dyes and other products such as dispersants, leveling agents, acids, alkalis, salts and sometimes heavy metals. The wastewater contains natural impurities extracted from the fibres and a mixture of the process chemicals such as organic compounds, dissolved inorganic salts, dyes and heavy metals. In general, the effluent is highly-colored and is alkaline in nature. This study is focused on investigating the characteristic of effluent from textile industry. The ranges of the physico-chemical parameters studied were as follows: pH 6.37-11.84, total dissolved solids (TDS) 601-2450 mg/l, suspended solids (SS) 1.80-183.3 mg/l, ammonia 0.2 mg/l-21.4 mg/l, chromium 0.2-214.4 g/l, lead 1.4-756.3 g/l, copper 4.69- 436.5 g/l, zinc 0.2-352.7 g/l, nickel 2.46-986.5 g/l, cadmium 0.13-17.77 g/l and their analysis highlighted the degree of pollution of wastewater resulted from textile industry. Keywords: wastewater, textile industry, characterization, polluant The 18 ICIT National Conference Progress in Cryogenics and Isotopes Separation
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PREPARATION METHODS FOR TRITIUM LIQUID SCINTILLATION ANALYSIS FROM ENVIRONMENTAL SAMPLES Carmen Varlam1, Irina Vagner1, Daniela Marinescu2, Ionut Faurescu1, Denisa Faurescu1, Diana Bogdan1
1
National Institute for Cryogenics and Isotopic Technologies, Rm. Valcea, 4 Uzinei Street 2 OLTCHIM S.A. Research Center Rm. Valcea, 1 Uzinei Street
ABSTRACT
The ways in which the Experimental Pilot Plant for Tritium and Deuterium Separation (PPTDS research unit with tasks in developing technologies for tritium and deuterium separation from heavy water using cryogenic distillation), can interact with the environment are: by atmospheric release and through the sewage system. For establishment of the base level of tritium concentration in the environment around PPTDS we elaborate some methods for preparation and measurement of tissue free water tritium (TFWT) and organically bond tritium (OBT) in different types of environmental samples (grass, potatoes, apple, milk). Within plants and animals, tritium exists as either tissue-free water tritium (TFWT) or organically bound tritium (OBT). For the measurement of TFWT in environmental samples, methods such as lyophilization (freezedrying)1 and azeotropic distillation2 were used. For OBT measurement dried samples were combusted in a Parr combustion bomb (Model 1121)1. Some methods for purification of combustion water were investigated1,3,4. Determination of environmental tritium concentration was carried out using liquid scintillation counting (LSC), with ultra-low liquid scintillation spectrometer Quantulus 1220.
REFERENCES 1. Kim S.B., Roche, J., 2012. Organically bound tritium (OBT) measurement method to suit the COG members. COG-RD-PRO-002 2. Varlam, C., Stefanescu, I., Faurescu, I., Vagner, I., Faurescu, D., Bogdan, D., 2011. Establishing routine procedure for environmental tritium concentration at ICIT. Romanian Journal of Physics 56 (1-2), 233-239 3. Kotzer, T.G., Workman, W.J.G., 1999. Measurements of Tritium (HTO, TFWT, OBT) in Environmental Samples at Varying Distances from a Nuclear Generating Station. AECL-12029 4. Paunescu, N., Galeriu, D., 2003. Report WP3 IDRANAP 44-03/ 2003
EVALUATION OF THE DEUTERIUM MODULATION POTENTIAL OF LEAD STATUS ON Zea mays ORGANOGENESIS AND GROWTH Gallia Butnaru1*, Ioan Sarac1, Gheorghe Titescu2, Horia Butnariu1**
2
Banat University of Agricultural and Veterinary Medicine from Timisoara National Institute for R&D for Cryogenics and Isotopic Technologies ICIT RM. Valcea * Academy of Romanian Scientists; **Academy of Agricultural and Forestry
ABSTRACT
The experiment was carried out in lab conditions [germination and embryogenesis], and in field in 2011 and 2012. In controlled lab conditions, the results pointed out the interaction among genotypes, D concentration associated with lead. The change in deuterium concentration associated with lead affected germination, root and coleoptile & 150 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
E nv nm en nt al an nd dL eQ ua al En vi ir ro on me ta la Li if fe Qu li it ty y embryo-leaves formation. The germination on three maize lines [521, 555, 522] was significantly different, pointing out the genotypes different strong response. The most sensitive was the genotype 555. It was significantly reduced in comparison to 521 and 522 [d= - 31.18 and d=34.17 > 0.01]. The weak particularity continued along the entire life cycle. Generally the germination was significantly repressed by lead amount [50, 100 and 200 ppm]. The association between deuterium depleted water [30 ppm] and a high amount of lead [200 ppm] was an exception - the germination was significantly stimulated [d=20 and d=16.7 > 0.01]. The low content of D revealed a favorable modulation effect. The embryonic organogenesis was slow. The root growth was significantly repressed by the low amount of D [d= - 0.23 > 0.5]. The coleoptiles growth was not influenced by D&Pb. The plantlets adaptation in field conditions was dramatically reduced. More than 60% of them could not survive. The comparison between 2011 and 2012 of the plants growth and their traits emphasized the capacity of restoring their repressed status. In comparison to D 145 ppm the D30 the plants characteristic elements were superior developed. The yield quality was differently influenced by D&Pb amount. The 1000 kernel weight was higher on D-30 plants [241>239 g]. The protein content was higher when the seeds were germinated in low amount of D. On the other hand, the oil and starch synthesis were repressed. We consider that D content is working as a modulator in different synthesis pathways. Keywords: amount of D & lead concentration; germination, organogenesis, plant growth, plants trait
AEROSOLS ON THE BLACK SEA SHORE: A STUDY USING SUNPHOTOMETER MEASUREMENTS Sabina Stefan1, Gabriela Raducan2
University of Bucharest, Faculty of Physics, Department of Earth Sciences, e-mail: sabina_stefan@yahoo.com; 2National Institute for Research and Development for Cryogenics and Isotopic Technologies ICIT- Rm. Valcea, Romania, e-mail: gabi_raducan@yahoo.com
1
ABSTRACT
The aim of this study is to present the results of the sunphotometer - measured aerosol optical depth (AOD) on the Black Sea shore which were done in the autumn of 2009 for two months. The temporal, spectral and spatial variations of AOD are investigated. The relationship between AOD and relative humidity and variations in AOD and the Angstrom exponent with respect to the prevailing wind conditions has been presented. The interaction (scattering as well as absorption) of solar radiation by atmospheric constituents is strongly dependent on the nature of particles, size of particles, as well as the wavelength of radiation. By knowing the aerosol optical depth we can estimate the size of suspended particles. The sunphotometers offer an inexpensive as well as convenient way of measuring aerosol optical depth.
151
PARAMETERIZATION OF THE BACKGROUND CONCENTRATION TO IMPROVE THE OSPM PERFORMANCE Gabriela Raducan
National Institute for Research and Development for Cryogenics and Isotopic Technologies ICIT- Rm. Valcea, Romania, e-mail: gabi_raducan@yahoo.com
ABSTRACT
Air quality in urban areas continues to represent a major concern, taking into account the impact of pollution on environment and human health. Air quality study involves researchers of several scientific disciplines and requires the development of theoretical, practical and methodological concepts, always new, for understanding, controlling and combating urban air pollution. Together with monitoring, modeling air pollution is a very important tool in the management of air quality. It enables efficient verification in order to reduce emissions and make predictions of pollution levels associated with changes in urban infrastructure. The aim of this research is to improve the OSPM performance using a parameterization relationship. The Danish Operational Street Pollution Model was applied in a street canyon from Leicester, for the period January to March 2005, in 7 points of the street, located in different heights from the ground. To improve the model performance a simple empirical relationship for parameterization of hourly background concentrations was established. The correlations between the modeled and the measured data were improved, so parameterization has been validated for this set of data.
SYNTHESIS AND CHARACTERIZATION OF HIGHLY ORDERED SBA-15 FOR RETENTION OF POLYPHENOLS FROM RED WINE Violeta Niculescu1, Andrea Iordache1, Roxana Ionete1, Nadia Paun1, Viorica Parvulescu2
National Institute for Research and Development for Cryogenics and Isotopic Technologies- ICIT Rm. Valcea, 4 Uzinei St., 240050 Rm. Valcea, Romania, violeta.niculescu@icsi.ro; 2Ilie Murgulescu Institute of Physical Chemistry, Romanian Academy, Splaiul Independentei 202, 060021, Bucharest, Romania, vpirvulescu@icf.ro
1
ABSTRACT
Since the discovery of highly ordered M41S family mesoporous molecular sieves in 1992, considerable attention has been focused on tailoring the chemical composition of these materials via the surfactant templated hydrothermal synthesis [1, 2]. Highly ordered large pore SBA-15 was synthesized by co-condensation of tetraethylorthosilicate (TEOS) and 3-aminopropyltriethoxysilane (APTES) using an amphiphilic block copolymer as the structure-directing agent. This mesoporous material exhibits a type IV nitrogen adsorption-desorption isotherm and has a specific surface area of 1108 m2/g. The adsorption properties of the calcined mesoporous silica SBA-15 material, as a consequence of the presence of silanol groups that are active sites for adsorption, were evaluated in the clarification process of two types of red wines. The purpose of this study was the investigation of the total polyphenols content (reduction), the selectivity and stabilization for some compounds (phenolic acids, epicatechin, catechin) and the chromatic characteristics of wine.
152
REFERENCE [1] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Frederichson, B. F. Chmelka and G. D. Stucky, Science, 279, 548 (1998). [2] A. M. Silvestre-Albero, E. O. Jardim, E. Bruijn,V. Meynen, P. Cool, A. SepulvedaEscribano, J. Silvestre-Albero, F. Rodrguez-Reinoso, Langmuir, 25, 939 (2009).
ENVIRONMENTAL IMPACT OF PRIORITY HAZARDOUS SUBSTANCES ACCUMULATING IN SOIL, WATER AND SEDIMENT IN THE INDUSTRIAL AREA OF RAMNICU VALCEA Mihaela Iordache1,2, Ioan Viorel Branzoi2, Ioan Iordache3*, Georgeta Totea2, Nicoleta Georgeta Dobre2
1
National Research and Development Institute for Industrial Ecology Ramnicu Valcea Subsidiary, 1 Uzinei St., tel./fax: +40 250 73 75 43, e-mail: ecoind@vl.ro; 2Polytehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7, Polizu Street, Sector1, Bucharest, 011061, Romania; 3 National Institute for Research and Development for Cryogenics and Isotopic Technologies- ICIT, Rm Valcea, 4 Uzinei St.,240050, *corresponding author: iordache.ioan@icsi.ro
ABSTRACT
The main pollution source may generate hazardous substances in the industrial platform area is S.C. Oltchim S.A. Soil pollution research priority hazardous substances in the industrial area of platform Rm. Valcea were soil samples collected inside S.C. Oltchim S.A. and quality indicators studied were: pH, cadmium, nickel, copper, 1.2 dichloroethane, trichloroethylene, perchlorethylene, 1.2.4 trichlorobenzene, analyzes were compared with the Order no. 756/1997. Olt River assessing water quality in upstream and downstream of discharges Valcea chemical platform, samples were harvested water / sediment from sections Priza Olt, Cremenari, Bbeni Marcea and comparing results with requirements Order No.161/2006 . The results show that heavy metals in sediments collected from the Olt River, (Priza Olt and Cremenari), had higher concentrations than in National Legislation. Also notice that in all three points, 1.2 dichloroethane, trichlorethylene, 1.2.4 trichlorobenzene and perchlorethylene taking values below the detection method. Concentrations of heavy metals in water were lower than the limits imposed by National Legislation. For organochlorine substances analyzed in three points, an increase of concentration for 1.2 dichloroethane, trichloroethylene and perchlorethylene in sections downstream of the chemical platform of Ramnicu Valcea (Cremenari and Babeni Marcea) to the Priza Olt upstream section of the platform. The concentrations of nickel, copper, cadmium, 1.2 dichloroethane, trichlorethylene, 1.2.4 trichlorobenzene and perchlorethylene in soil samples respect the limits by the Environmental Legislation. KEYWORDS: priority hazardous substances, organochlorine substances, heavy metals, water surface
ACKNOWLEDGMENTS The authors acknowledge the support provided by Project: Doctoral Scholarships: Investment in research and innovation and development for the future (DocInvest), Project cofinanced by European Social Fund Operational Programme Human Resources Development 20072013, ID 76813.
CONSIDERATIONS CONCERNING THE INFLUENCE OF B20 BIODIESEL BLEND ON URBAN BUSES OPERATION AND MAINTENANCE Adrian Roca1, Daniela Roca2, Gabriel Vldu3
University of Craiova, Faculty of Agriculture and Horticulture; 2)University of Craiova, Faculty of Electrical Engineering, 13, A. I. Cuza Street, Craiova, Phone / Fax: 0251.414.541, e-mail: adrosca2003@yahoo.com; 3) Research -Design Institute for Automation IPA Craiova, 12, Stefan cel Mare Street, Craiova, Phone/Fax: 0251.418.882, e-mail: office@ipacv.ro
1
ABSTRACT
The paper presents experimental research results concerning the influence of B20 biodiesel blend on urban buses operation and maintenance in Craiova city. There are presented original data by using thermovision to determine correlations between B20 biodiesel blend fuel used in buses engine and, the engines temperature. There are presented potential incompatibilities between B20 biodiesel and common elastomers used in seals and hoses. Keywords: B 20 biodiesel blend, thermovision, wear friction, biodiesel incompatibilities.
ANALYSIS OF IDEALIZED TROPICAL CYCLONE SIMULATIONS USING THE WEATHER RESEARCH AND FORECASTING MODEL Gabriela Raducan, Roxana Elena Ionete, Ioan Stefanescu
National Institute for R&D for Cryogenics and Isotopic Technologies ICIT Rm. Valcea, 4 Uzinei Street, 240050, Rm. Valcea, Romania, e-mail: gabi_raducan@yahoo.com
ABSTRACT
In this study simulations of WRF-ARW (Advanced Research WRF) model, version 3.4 were done to analyze the sensitivity of tropical cyclone size to the environmental humidity and pressure. The resolution of all simulations was of 36 km, to model the tropical phenomena. A cloud resolving nest at 4 km resolution was used over the Pacific warm pool, which is the heat engine of the tropics, to analyze some tropical convection parameterizations. WRF reasonably captures various tropical modes including the eastward traveling Kelvin waves which play an important role in the dynamics of El Nino-Southern Oscillation and are often associated with anomalies in surface wind stress. The size of the simulated tropical cyclone exhibited considerable variation with environmental humidity, more moist environments being associated with larger storms. Also, a monotonic variation between the SST (sea surface temperature) and the tropical cyclone size could not be established and the changes in convection schemes have little impacts on the tropical cyclone size.
154
BIODIESEL PRODUCTION USING MICROALGAE T. A. Costache, L. Popovici, I. Stamatin

University of Bucharest, Faculty of Physics, 3NanoSAE research center
ABSTRACT
The poster shows the results obtained by cultivating collected samples of different types of water river and marine for the development of microalgae, and treatment of obtained cultures for the production of biodiesel. Initially the microalgae were grown in flasks under aeration and illumination; subsequently a tubular bioreactor with water pump was designed and built. The obtained biomass was dried, and the lipid content of the cells was extracted with an appropriate solvent. Following transesterification with sodium methoxide biodiesel was obtained. This print illustrates the amount of biomass grown, quantity of biodiesel obtained, and a comparison between the productivities of the two cultivation methods: aerated flasks vs tubular bioreactor. Also, the benefits of replacing mineral oil with biodiesel and the advantages of using microalgae vs land crops are shown.
155
Laboratory Analysis Methods
L ab at An na al Me et ho ds La bo or ra to or ry y A ly ys si is s M th od s
ACTIVE THERMOGRAPHY NON-DESTRUCTIVE & NON-CONTACT MATERIAL TESTING Marius Popovici

Micronix Plus SRL, Str. 1 Mai nr. 2, Otopeni, 075100, Jud. Ilfov Tel. 021 314081, 82 Fax 021 3124083 Email: mpopovici@micronix.ro
ABSTRACT
Active Thermography (AT) is a package of methods who use thermal cameras to make visible internal defects, surface cracks and material stress. Currently, they are several techniques based on active thermography: lock-in, pulse, transient, vibro and thermal stress analysis. Depending on the inspection task, one or more methods are used. This paper will give a brief overview of each method and will introduce several IR cameras suggested to be used in AT systems. Keywords: active thermography, lock-in, thermal camera, thermovision, thermal stress analysis
COMPOUND-SPECIFIC CARBON ISOTOPE ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS USING GAS CHROMATOGRAPHY COMBUSTION ISOTOPE RATIO MASS SPECTROMETRY GC-C-IRMS Diana Costinel, Geana Irina, Ionete Roxana, Dinca Oana
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no.4; P.O. Box 7 Rureni, 240050, Rm.Vlcea, Romania, e-mail: diana@icsi.ro
ABSTRACT
Mastering the isotopic tool in Environmental science, from analytical developments to the modeling and understanding of both natural and industrial processes, is an important part of the conception of a sustainable development in the world. By joining the mass spectrometry with gas chromatography, the separation of individual organic compounds in a mixture is allowed, followed by combustion of each separate organic compound to carbon dioxide and then determination of the isotopes ratio in the carbon dioxide. This paper intend to give a brief view on gas chromatography GC coupled with stable isotope ratio mass spectrometry IRMS as an important analytical technique to investigate the carbon isotopic composition of polycyclic aromatic hydrocarbons, to determine the origin of these components, useful to identify the sources of pollution as a result of environmental accidents or their biodegradation rates in the environment. Keywords: stable carbon isotopes, polycyclic aromatic hydrocarbons, gas chromatography combustion isotope ratio mass spectrometry GC/C-IRMS
159
L ab at An na al Me et ho ds La bo or ra to or ry yA ly ys si is sM th od s
AN OVERVIEW OF ANALYTICAL TECHNIQUES FOR PETROLEUM HYDROCARBONS CHEMICAL FINGERPRINTING Irina Geana, Raluca Popescu, Diana Costinel, Roxana Elena Ionete
National Institute for Research and Development for Cryogenic and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no.4; P.O. Box 7 Rureni, 240050, Rm.Vlcea, Romania, e-mail: irina.geana@icsi.ro
ABSTRACT
Due to the major development of crude oil industry it is very important to identify the source of the natural petroleum in order to improve the quality of products and to ensure the large variety of consumers of its authenticity. Literature provides other aspect of this type of analysis that is based on extensively damages caused by the oil spills upon the human health, marine life, terrestrial life and natural resources. Gas chromatography technique coupled with mass spectrometry was used because of the highly complex hydrocarbon compound and this method led to a better knowledge of the hydrocarbon composition type of petroleum. In order to obtain specific, accurate and successful oil fingerprinting results from petroleum analysis it is very important to characterized, link them to the known sources, appropriate sampling, analytical approaches and data interpretation strategies. This article highlights the most recent development and advances of chemical analysis methodologies which are most frequently used in oil spill characterization and identification studies. Keywords: petroleum hydrocarbons, oil, gas chromatography, fingerprinting.
ASSESSMENT OF THE ENVIRONMENTAL FATE OF -HEXACHLOROCYCLOHEXANE USING COMPOUND-SPECIFIC STABLE ISOTOPE FRACTIONATION ANALYSIS (CSIA) AND ENANTIOMER-SPECIFIC STABLE CARBON ISOTOPE ANALYSIS (ESIA) Silviu-Laurentiu Badea1,2
1
Department of Chemistry, Ume University, Ume, SE-90187, Sweden, Phone: +46-90-786 9323, Fax: +46-90-7867655, e-mail: silviu.badea@chem.umu.se; 2"Horia Hulubei" National Institute of Physics and Nuclear Engineering (NIPNE), Bucharest-Magurele, Romania
ABSTRACT
The carbon isotope ratios of the -HCH-enantiomers were determined for a commercially available -HCH using a gas chromatography-combustion-isotope ratio mass spectrometer (GC-C-IRMS) equipped with a chiral column [1]. The GC-C-IRMS measurements revealed -values of -32.5 0.8 and of -32.3 0.5 for (-) -HCH and (+) HCH, respectively. The -values of (-) -HCH and (+) -HCH, the isotope ratio of bulk -HCH was estimated with 32.4 0.6 which was in accordance with -values obtained by GC-C-IRMS (-32.7 0.2 ) and elemental analyzerisotope ratio mass spectrometry (EA-IRMS) of the bulk -HCH (-32.2 0.1 ). The similarity of isotope ratio of bulk analysis -HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the -HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The reproducibility of ESIA exhibited standard deviations (2) mostly < 0.5 . In order to test the chiral GC-C-IRMS method the isotope composition of individual enantiomers in biodegradation experiment of -HCH with Clostridium pasteurianum and samples from a contaminated field site were examined. The data set obtained from biodegradation experiment with -HCH with Clostridium pasteurianum did not allow quantifying the individual isotope fractionation factors for the enantiomers within an uncertainty needed for 160 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
L ab at An na al Me et ho ds La bo or ra to or ry y A ly ys si is s M th od s interpreting the specific mechanism of the carbon chlorine bond cleavage. More recently Bashir et al. (2012) [2] determinated the individual isotope fractionation factors for the -HCH enantiomers during aerobic biodegradation of -HCH by Sphingobium indicum B90A and Sphingobium japonicum UT26. They found a higher enrichment factor for (-) -HCH (C = -2 0.8 to -3.3 0.8). in comparison to (+) -HCH (C = -0.8 to 1). This variability in enantiomeric isotope fractionation may be due to different variants of HCH degrading enzymes (LinA1 and LinA2) [3] and/or varying rate-limiting effects. The isotopic composition of -HCH enantiomers show a range of enantiomeric and isotope pattern suggesting that enantiomeric and isotope fractioantion can serve as an indicator for biodegradation and source characterization of -HCH in the environment. Keywords: GC-C-IRMS, GC-MS, enantiomers, chiral column, EA-IRMS
REFERENCES 1. Badea, S. L.; Vogt, C.; Gehre, M.; Fischer, A.; Danet, A. F.; Richnow, H. H., Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of alpha-hexachlorocyclohexane in the environment. Rapid Commun. Mass Spectrom. 2011, 25, (10), 1363-1372. 2. Bashir, S.; Richnow, H. H.; Vogt, C.; Fischer, A.; Nijenhuis, I., Isomer and enantioselective carbon stable isotope fractionation of hexachlorocyclohexane (HCH) during aerobic biodegradation by Sphingobium spp. In Joint European Stable Isotope Users group Meeting JESIUM 2012, 2-7 September 2012 Leipzig, Germany, 2012. 3. Suar, M.; Hauser, A.; Poiger, T.; Buser, H. R.; Muller, M. D.; Dogra, C.; Raina, V.; Holliger, C.; van der Meer, J. R.; Lal, R.; Kohler, H. P. E., Enantioselective transformation of alpha-hexachlorocyclohexane by the dehydrochlorinases LinA1 and LinA2 from the soil bacterium Sphingomonas paucimobilis B90A. Appl. Environ. Microbiol. 2005, 71, (12), 8514-8518.
161
Agriculture and food safety
A Ag gr ul ur ea an nd d f ds af et ri ic cu lt tu re fo oo od sa fe ty y
PHYSICAL AND CHEMICAL CHARACTERIZATION OF FLAVORED AND DEMY FLAVORED WINES FROM RECAS VINEYARD Ecaterina Lengyel1, Letitia Oprean1, Kettney Otto1, Ramona Iancu1, Bociu Diana2, Ovidiu Tita1
Lucian Blaga University of Sibiu, Faculty of Agricultural Sciences, Food Industry and Environmental Protection, Str. I. Raiu 7-9, 550012 Sibiu, Romania, E-mail: Ovidiu.tita@ulbsibiu.ro; 2National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania
1
ABSTRACT
Wine, the wonderful liquor resulted by means of complete or partial fermentation of the technologically processed grapes or of fresh must. It contains easy to assimilate substances like: sugars, ethylic alcohol, glycerin, organic acids, tannin, esters, aldehyde, proteins, amino acids, vitamins, mineral salts and others. All these elements award the wine with organoleptic qualities, aroma and savor. The present essay studies the physical and chemical aspects of the flavored and demy flavored wines in Recas vineyard, the following breeds being selected: Muscat Ottonel, Sauvignon Blanc and Chardonney. The analyzed wines, sweet, semi sweet and demi-sec have been obtained through the vineyards technology that has been applied during the year of processing. As a wine analysis selection criterion, years 2010 and 2011 have been taken into consideration, years with very rich crops from the climatic, quality and quantity aspects. The results that have been obtained led to situating the wines in the geographical indicationViile Timiului. Keywords: flavored wines, semi-flavored wines, physical and chemical properties
PHYSICOCHEMICAL AND MICROBIOLOGICAL CHARACTERISTICS OF BRANCOVEANU, GURA MINEI AND OCNITA LAKES, AS REPRE-SENTATIVE FOR THE LACUSTRINE COMPLEX FROM OCNA SIBIULUI Diana Bociu1, Ecaterina Lengyel2, Roxana Ionete1
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0040 250 732 744 (int 188), fax: 0040 250 732 746, E-mail: diana.bociu@icsi.ro; 2"Lucian Blaga" University of Sibiu, Faculty of Agricultural Sciences, Food Industry and Environmental Protection, Str. I. Raiu 7-9, 550012 Sibiu, Romania
1
ABSTRACT
This study evaluates the physicochemical and microbiological characteristics of the saline waters of three representative lakes from Ocna Sibiului in order to promote their therapeutic purpose. The water monitoring campaign of the three investigated lakes, Brancoveanu, Gura Minei and Ocnita, was done from May till October 2011 after the rehabilitation of the infrastructure and the arrangement of the lakes from Ocna Sibiului resort requested by the Local Council of Ocna Sibiului from the Central Agency of Regional Development. Sampling was done twice a month (at every two weeks) at an approximate depth of 40 cm. Measurements were performed to emphasize the level of mineralization, organic load and the concentration of mineral substances. From the microbiological point of view the total number of mezofili germs which develop at 22C respectively 37C was pursued. The results led to a physico165 The 18th ICIT National Conference Progress in Cryogenics and Isotopes Separation
A Ag gr ul ur ea an nd d f ds af et ri ic cu lt tu re fo oo od sa fe ty y chemical and microbiological specific profile for these lakes which are recommended to be used for bathing, therapy and leisure. Keywords: hypersaline waters, pH, mineral substances, temperature, conductivity
WINE QUALITY ASSURANCE USING MASS SPECTROMETRY TECHNIQUES Oana Romina Dinca, Roxana Elena Ionete, Diana Costinel
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania, phone: 0250/732744; fax: 0250/732746; E-mail: oana.dinca@icsi.ro
ABSTRACT
Wines produced in different geographical regions will each have their specific character dictated by the climate, latitude and altitude. In wine authentication a key issue is to find suitable markers such as oxygen, carbon and strontium stable isotopes which record the isotopic composition of the vine source of water and the climatic condition experienced by the grape vine. These stable isotopes have been explored extensively to detect wine adulteration or for proving the claimed origin. Also, wine aroma is a very important parameter in terms of rigorous quality requirements. This work gives an overview on the most sensitive techniques applied for wine fingerprinting, considering information about environmental and technological aspects of wine geographical authentication. Keywords: wine, stable isotopes, fraud detection, ICP-MS, IRMS, GC-MS.
166
Addendum
A Ad dd de en nd du um m
HYDROGEN - PAST, PRESENT AND FUTURE Ioan Stamatin

University of Bucharest, Faculty of Physics, Bucharest, Romania
USE GIS TEHNIQUE TO ENVIRONMENTAL MONITORING IN AN INDUSTRIAL ZONE AND A GREEN AREA Gili Saros, Diana Florescu, Irina Geana, Raluca Popescu, Andreea Maria Iordache, Roxana Ionete
National Institute for Research and Development for Cryogenic and Isotopic Technologies ICIT Ramnicu Valcea,Uzinei Street, No. 4, PO Box 7 Raureni, 240050, Rm. Valcea, Romania E-mail: gili@icsi.ro, andreea.iordache@icsi.ro, vraluca@icsi.ro ABSTRACT
Analysis of the data and modeling them through the system GIS represents one of the steps in the future for environmental monitoring. The purpose of this study is to achieve a comprehensive system of monitoring the quality of the environment through investigations of pollutants in the air, water, soil, from an Industrial Area and compare it to a Green Area. We have used GIS technique to make maps of impact and for the distribution of certain concentrations of important environment pollutants, registered as and the points of harvesting, and default ability to represent their evolution in time for the purpose of establishing quality of the environment. Keywords: environmental monitoring, GIS, maps
INSTALATIE PILOT PENTRU PRELUCRAREA PRIN DISTILARE IN VID A ULEIURILOR MINERALE UZATE. TESTE PRELIMINARE PILOT PLANT FOR PROCESSING USED MINERAL OILS BY VACUUM DISTILLATION Floarea Pop, Cornelia Croitoru, Emil Zaharia1, Dorin Bombo2, Elisabeta Pop1
2
Atica Chemicals SRL, 202 Cazanesti Str., Rm. Valcea, Romania Petroleum - Gas University of Ploiesti, 39 Calea Bucuresti,100520, Ploiesti, Romania e-mail: cica_pop_romania@yahoo.com
ABSTRACT
In accordance with settlements in force, recovery of used oils can be performed only by methods that generates not pollutants above maximum rated value. Vacuum distillation is a non-pollutant technology for recovery used oils. It obtains products (distillate, residue) that are used to prepare storable hydrocarbon pavement mixture and bituminous emulsions, respectively. The 18th ICIT International Conference Progress in Cryogenics and Isotopes Separation 169
At ATICA CHEMICAL SRL it was experimented separation of light components from used mineral oils by vacuum distillation. First experimental data, obtained at laboratory scale, in a glass column, were used for design a pilot plant, whose distillation column has a diameter of 311 mm and is equipped with ring packing. Preliminary tests were performed on this plant, as batch distillation, at pressures in range of 30-38 mmHg. During experiments
temperature at column top increased from 240 to 290oC. The quality of products extracted at top and bottom of distillation column satisfy indicated usage domain. The paper presents laboratory experimental data, flow diagram of the pilot plant, design data of distillation column and preliminary tests on pilot plant.
170
The 18th ICIT International Conference Progress in Cryogenics and Isotopes Separation
CERNAVODA NPP SOURCE TERM AND DOSE REDUCTION Catalina Chitu, Ioan Plaesu, Ion Popescu
CNE Cernavoda NPP, No. 2, Medgidiei Str. Cernavoda 905200, Romania phone: 4-0241-239-340; fax: 4-0241-239-929, e-mail: Catalina.Chitu@cne.ro; Ioan.Plaesu@cne.ro; Ion.Popescu@cne.ro
ABSTRACT
At Cernavoda NPP U2, with commercial operation in the fall of 2007, was implemented the Radiation Monitoring System (RMS). By implementing this system the collective dose of the operating personnel is expected to be reduced by minimizing the need to enter into high radiation areas. Also, a better radiation hazard control is provided for the normal operation of the plant, as real time radiation hazard information are available. The purpose of the Radiation Monitoring System is to interface the radiation monitoring equipment to a computerized system that allows remote monitoring, limited remote control capability and maintain integrated short and long-term database. Information is transferred in real time using standard communication protocols and commercial computers. RMS interface with the following systems: Fixed Gamma Area Monitoring, Fixed Contamination Monitoring, Portable Radiation Monitors, Fixed Tritium in Air Monitoring, Liquid Effluent Monitor, Gaseous Effluent Monitor and Post Accident Air Sampling. Tritiated water vapor is a health hazard and its early detection in nuclear plants is important because it has all the characteristics of water vapour in atmosphere. By detecting tritiated vapour, the Fixed Tritium in Air Monitoring system serves the following purposes: fast detection of D2O leaks in the monitored areas; - savings of the tritium surveys costs (lab consumables and manpower); - Improving station dose performance indicator.
The 18th ICIT International Conference Progress in Cryogenics and Isotopes Separation
171

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The 18th ICIT Conference PROGRESS IN CRYOGENICS AND ISOTOPES SEPARATION

Calimanesti-Caciulata, Romania October 25-26, 2012

Tehnoredactare: Camelia Asprita Coperta: Camelia Asprita ISBN: 978-973-750-228-5

SECTION 1: Stable Isotopes Physics. Technologies and Applications

SECTION 2: Cryogenics Technologies and Equipments

SECTION 3: Science and Materials Engineering

SECTION 4: Nuclear Power - fission and fusion

SECTION 5: Hydrogen and Fuel Cells

SECTION 6: Environmental and Life Quality

SECTION 7: Laboratory Analysis Methods

SECTION 8: Agriculture and food safety

NITRIDE NUCLEAR FUELS Damian Axente

RESERVED TITLE Mihai Varlam

RESERVED TITLE Liviu Stefan

Stable Isotopes Physics, Technologies and Applications

Cryogenics Technologies and Equipments

a. The superconducting magnet system.

2nd stage 0.35 0.12 1.02 1.49

Symmetry planes (adiabatic)

Shields surfaces (surface to surface radiation)

Twarm = 50 K Tamb = 300 K

3 2.66 T 2.5 |B0| [T] 2.13 T 2 1.60 T

150 Isupply [A]

CELIN SRL, Bucuresti; 2Asociatia pentru Automatizari si Instrumentatie din Romania

Science and Materials Engineering

(corr .rate) abs .inh. (corr .rate) inh. (corr.rate )abs.inh

TD2 uninh. TD6 (0.0005M TEA) Ts13 uninh.

Weight loss (mg/cm2)

Ts15( 0.0005M TEA)

-12 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

SA 106 F-TD2 SA 106 F-TD8

Weight loss (mg/cm2)

-12 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

SA 106 F-T11 SA 106 F-T13

SA 106 F-T12 Weight loss (mg/cm2)

S en nc ea an nd dM Ma at er al ng gi ne ee er ng g Sc ci ie ce te ri ia ls sE En in ri in Keywords: Thermal cycling, uranium zirconium hydride, thermo-gravimetric

UM bar C % % m3/h hour hour

Values 10-21 30-135 H2O-H2S; H2 moist 3,5-4,5 Min.99,8 1,5-7,5 2304 54

Figure 1. As received sample, G52-28

Figure 2. G52-28, CC, after testing

Figure. 3. G52-28, HC, after testing

Figure 4. Carbon steel, as received sample: ferrite+pearlite

Figure 5- Carbon steel, HC sample: ferrite+pearlite

Figure 6- Carbon steel, CC sample: ferrite+pearlite

Figure 7. Stainless steel, as received sample: austenite+carbides

Figure 10. HC carbon steel: micro-cracks, porous layer+compact

Figure 11. CC carbon steel: porous external layer+corrozive penetration in substrate

Figure 12. CC stainless steel, thickness layer 35-38 m (centre)

Figure 13. HC stainless steel, thickness layer 25 m (centre)

Table 2. Hydrogen content, [3]

Nuclear Power fission and fusion

UTS (MPa) 545 564

25mm (%) 60.00 61.00

average standard dev minimum maximum average standard dev

245 7.8 218 231 222 6.3

288 9.4 270 285 277 6.6

556 7.8 545 562 554 7.6

60.40 0.42 58.00 60.80 59.10 1.24

0 YS 0.2% YS 1% UTS elon Mechanical Properties

Figure 5. Tube microstructure, longitudinal direction, average grain size = 42m

Figure 6. Tube microstructure, transverse direction, average grain size = 49m

2.5 HB/187.5kgf 150,149,148,149,148 148,150,150,145,148 151,148,151,150,148 150,151,148,150,148

HB Mean Value 149 148 150 149

Institute for Nuclear Research, Romania, 2CEA Saclay, France