RECOMMENDATIONS TO THE READER The presentation of a systematic collection of information about technology production of traditional ceramic materials, in particular

pressed tiles, presents many problems, since the very diverse cultural activity work of possible users of the information gathered. It could be conceived as a user to access, descriptive of the operations and machines, apart from a deeper understanding of the materials and problems, or, conversely, as a text of a deepening of technological operations, the result of which is taken for granted. The reader with a technical-scientific would led to search for specific news, innovative and original, or at least a collection of difficult to find information in condensed form, the player with activities technical productive would, however, affected by a manual resolution of the problems that daily beset the production line. The young technician, recently screened in the bowels of a production process, which little or nothing has been taught during the academic year of study or academic research, probably an overall picture that, with descriptions and required more than enough, led him to understand what happens in the "Factory", from the arrival of raw materials to packaging of finished products. To say that this volume is to be published soon, remember that the processes production try to reconcile all these different needs is not guilty of presumption: it would say that these books have to balance the demands described. Here it is, instead, made a serious attempt to describe the best, albeit briefly, a production line, ignoring the basics of descriptive and scientific matters, giving substance to a first volume that is talked about what happens during the individual stages of production process, and, in particular the importance of defining the property nature of the raw materials used, their meaning in a body and the problems they can generate, in addition to a general overview of the possible products, according to their technological characteristics. A brief introduction describes the main themes of the joints after developed. The second volume, however, is intended to further clarify aspects technology of each stage of the production process, through not so much a specific description machines, doomed to become obsolete in a short time, or through an explanation of the purpose and operation of each machine to effects of the final product. In this sense, a lot of space is given to

discussion of each stage of the casting defects in workmanship and a general framework Correlation between the defect in the final product and the production stage in which the defect has been generated. The cutting of the information will be available, as we said, on the production of pressed tiles, but more information will be different provided on other technologies or products, if it leads to better understanding of reaction mechanisms. A large collection of tables and usability standards completes the work.

INTRODUCTION o start talking ceramic technology is certainly useful to introduce some key definitions to provide guidance in this area primarily by defining what is meant by ceramide. In fact, what is actually a ceramic material? Among dozens of possible definitions, a ceramic material can be described effectively as "any product which has a shape composed of materials inorganic non-metallic raw (both mineral and synthetic), which from a dust inconsistent state is transformed by means of various operations on a product semi, which, by cooking, it becomes a solid object, which has a structure partly crystalline and partly glassy. " After cooking, virtually all the transformations and / or combinations are permanent. When we speak of inorganic materials is necessary to consider the degree of abundance the most common Earth's crust, as to make pottery, is obviously desirable and advantageous to use the most common raw materials and economic.

Figure 1 shows that we are talking mainly of silicon and aluminum oxides, as well as with different contents of Fe, Ca, Mg, Na and K, which are effectively the first 7 most abundant elements in nature and the elements are always present in a ceramic paste. By observing, then the Periodic Table of the Elements, Table 1, PERIODIC TABLE OF THE ELEMENTS

We really appreciate the small number of items of interest related with a ceramic body (Al, Si, Ca, Mg, Fe, Ti, Na and K), even when consider the main constituents of the enamel (eg. Pb, Zn, Sn, Zr, Cr, Ni, Cr, V, B, etc.), It is clear how narrow is the range of elements

necessary to characterize a traditional ceramic material. Indeed, in the spirit of this generic introduction on these materials, we can define the field of study and that the products are mostly limited by composed of natural oxides, ie - CERAMIC TILES. - HEALTH. - CROCKERY. - CONCRETE. - SOME TYPES OF REFRACTORIES. Another approach is necessary for the special ceramic material or ADVANCED, which are usually composed of non-special-oxides or oxides: bioceramics, electrical and technical porcelain, ceramics for electronics, catalysts, special refractories, etc. Therefore, for a better understanding of the composition of a material traditional ceramic, we can generalize the composition of a ceramic paste, knowing that, with appropriate modifications, we can considerations similar to other traditional materials, the paste will be made From - Clay materials, which provide enough plasticity for to obtain a definite shape. These bring Al, Si and part of Ca, Fe, Ti. - Flux materials such as feldspar, nepheline etc., That the Cooking generate glassy phases that act as binders between the particles and promote solid-solid reactions, are carriers of Na, K, Al, Si. - Other materials such as talc, silica, pyrophyllite, CaCO3, etc.. (Called "INERT"), which can obtain specific performance, contributing mostly Ca, Mg, Si. - ADDITIVES primarily to improve the rheology of aqueous suspensions; can be inorganic or organic, and introduced into the paste in quantities very small (<1%). Wanting to briefly summarize the main effect of each chemical component present in the pulp for the production of ceramic tiles, we can say that the presence of oxides provides: Al2O3 refractory and plasticity (when associated with the presence of clay materials)

SiO2 structure, skeleton, and newly formed phases Fe2O3 and TiO2 smell and sometimes melting properties MgO CaO and control of contraction through the formation of calcium and magnesium silicates K2O and Na2O fluxes, which form glassy phases Al2O3 refractory and plasticity (when associated with the presence of clay materials) SiO2 structure, skeleton, and newly formed phases Fe2O3 and TiO2 smell and, Although this description of the features ceramic composition chemistry brings to the pasta, is a proven fact that the same chemical analysis a ceramic substrate or raw material is not the most important data for the characterization of the product: it can be shown products easily technically very different, for its use and technical characteristics pavers as low water absorption compared to the tiles, health, bricks, etc., have very similar chemical analysis. Any major effect may be the proportion of Ca and Mg, which leads to a differential contraction done: in fact, the higher the content of these elements, the smaller is this effect, as it silicates are calcium and magnesium to increase its volume with temperature, in contrast to contraction due to the collapse of the silicate phases. Figure 2b shows a example of state diagrams, which serve to establish a balance between the various components. Figures 3 through 8 below, you can see a good example of this

Table 2a. Composition and characteristics of different types of pasta. ehavior where, in the form of ternary diagrams, represent the areas compositional types of product such as the tiles (covering

low shrinkage), pieces of red paste type cottoforte "or fired tile strong (Intermediate behavior, the high water absorption) and stoneware (high shrinkage and low water absorption). [It is recalled that permits the identification of ternary diagrams in a system in equilibrium, For example, the composition of systems of three components, represented in percentages variables, according to the schema below (Figure 2b): the composition of a any point in the resulting triangular diagram is given by the intersection in parallel with the sides of the triangle that cut through and which side represents A percentage value on the left side, on the basis of B and C on right side. For example, in the figure, the point P represents a composition of 30% A (E) + 20% of B (F) + 50% C (G)].

Figure 2b. Reading the percentage composition of the axes of a triangular diagram.

Figure 3. Ternary diagram with the compositional field SiO2/Al2O3/Fe2O3 total pastes majolica, stoneware and red cottoforte (Vincenzini and Fiori, 1977 / 2).

Figure 4. Ternary diagram K2O/MgO Fe2O3/Na2O + + CaO with compositional fields pastes majolica, stoneware cooking cottoforte and red (Vincenzini and Fiori, 1977 / 2).

Figure 5. Ternary diagram SiO2/Al2O3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O with compositional fields of red stoneware pasta and white stoneware potassium and sodium (Fabbri and Fiori, 1983 / 1).

Figure 6. Ternary diagram Al2O3/Na2O / K2O with compositional fields pastes red sandstone and white sandstone potassium and sodium

Figure 7. Ternary diagram K2O/TiO2 Al2O3/Na2O + + Fe2O3 + MgO + CaO with fields compositional pastes of red sandstone and white sandstone potassium and sodium

Figure 8. Ternary diagram TiO2/Fe2O3 SiO2/Al2O3 + + MgO + CaO + Na2O + K2O with compositional fields of clay majolica, stoneware and red cottoforte In order to effectively describe a raw material or a paste for ceramics, with relevant information on technological behavior, it then much rather use the mineralogical analysis (crystallographic) and sieve analysis. To better understand the utility of these techniques is necessary to consider how does a raw clay into a paste, as labor input plastic. In terms of a simple representation of the structure of a clay, we can consider that this is composed of a combination of units repetition SiO4, tetrahedral (T), associated with octahedral basic units Al (OH) 6, designated (O), 9 and 10;

Figure 9. Repeating units of the phyllosilicates

structural units SiO4 tetrahedral base + And octahedral base (Al (OH) +6 3 -.

Figure 10. Projection of the on the octahedral plane.

These are two-dimensional particles, the distance between two units repeating identical structural variable, depending on the type of material, such as example shown in Figure 11. Through this provision based on the repeating units, the space between two particles, micelles, or between two particles tapes etc., may vary from minimum of 2.7 (in the kaolinite) to a maximum of 8 or more Angstrom [1A = 10-8 cm], particularly chlorite, giving the possibility or not to incorporate molecules or foreign ions in the structure.

Figure 11. Examples of different spaced interreticulares that characterize raw materials clay.

The presence of water, in particular, between the particles means having the possibility of moving a particle over another, ie in practice to have plasticity. The presence of water, in particular, between the particles means having the possibility of moving a particle over another, ie in practice to have plasticity. Moreover, in these spaces, you can enter as ion flux Na + and K +, which will change the technological properties of raw materials. The presence of water, in particular, between the particles means having the possibility of moving a particle over another, ie in practice to have plasticity. It is therefore very important to know the mineralogy of clay content of a paste, in order to anticipate problems and advantages use: all this information can be obtained from diffraction techniques X-ray (XRD). The presence of water, in particular, between the particles means having the possibility of moving a particle over another, ie in practice to have plasticity. Considering now the flux materials, and mainly of feldspar, is, again, important to know the mineralogy, as formation temperature of the glass phase and the viscosity of glass are formed closely correlated with the type of feldspar, the feldspars (mineralogically defined as albite) have a higher melting temperature low, but also a low melt viscosity, while feldspars potassium (microcline, orthoclase, sanidine, etc.) have a higher viscosity, that can help in the case of dimensional sizes and bonding probleg problems during cooking. On the other hand, knowledge of the mineralogical nature individual raw materials of a paste helps the design characteristics specific, such as the formation of "eutectic", ie compositions individuals with lower melting points. The presence of water, in particular, between the particles means having the possibility of moving a particle over another, ie in practice to have plasticity. If we now turn to the particle size distribution, it is obvious that the objective of the formation and firing of a blank tile is to obtain a product that have been activated and completed the greatest number of reactions solid-solid, and this depends largely on the contact surface particles as the larger, more favors the development with temperature from sintering, through the reaction to the merger, as shown in Figure 12.

Figure 12. Schematic representation of a process sinterizacin.in. The clay particles themselves are small, but need to be mixed each other and with particles of other materials of suitable dimensions, taking

the city to obtain the maximum filling of space and, therefore, maximum density: this is achieved with an appropriate mix of different grain sizes. Therefore, to have good control of the fineness of a pasta is a simple enough residue on screen, but it would be advisable control with proper instrumentation, which is based on the principles of interaction of individual particles (diffraction, scattering, etc..) X-ray or laser. THE PRODUCTION PROCESS Regardless of the way to make the selection of raw materials to mix into a dough, to get the right mix, the production phases will invariably the following: - Selection, use and control of quarries. - Preparation of raw materials for mixing. - Preparation of pasta, by appropriate grinding. - Formation of the semi. - DRYING. - Several operations to add aesthetic value to the product. - COOKING. - CLASSIFICATION, PACKAGING AND STORAGE. Each of these phases requires attention and must be planned and executed with appropriate controls. The following outline describes the most common production process, phase by phase of the manufacture of ceramic tiles: PREPARATION OF PASTA dry Hammer Mill Pendulum mill Alsing wet mill (ball) Continuous Mill Desleidores Dry Pressed CONFORMATION Extrusion Cast Any decorations charges multiple, pressing Convection drying, slow or fast, radiation Cosmetic surgery usually glazed or applications special COOKING traditional (slow) or fast: for both techniques Single firing (support + enamel) Double-fired (baked enamel and media) Third, fourth fire etc. (Decorations, stickers) In the following tables (Tables 3-4) summarizes the production processes common.

Tables 3-4. Different production processes for the manufacture of ceramic tiles. If all phases of production have been well planned, can get the output of ceramic tiles plant. However: How and why

distinguish these tiles that can be used in various situations, from one airport to the bath house, from an operating room to a floor industrial, etc..? It is therefore necessary to introduce briefly the concept of classification ceramic tiles: Usually classified according to: INTERNATIONAL STANDARDS based mainly on the type production process, or the absorption water of the cooked and still, referring to USAGE OF TRADE using old classifications as Gres, Majolica, Clinker, etc. The correct approach, obviously, would be to take into account a complete set of technological characteristics of the fired pieces, main ones being: - Type of use (floor or wall covering - interior or exterior). - Absorption of water, but also resistance to freeze / thaw. - Contraction. - Resistance to bending. - Resistance to abrasion and stains. - Color of the paste. A thorough knowledge of all these parameters can actually define which belongs to a class ceramic tile, allowing its proper use. After rinsing, now in this kind of "summary" of introducing the argument in question, we go deeper into the subject to be treated, indicating research methodologies that could and would be suitable to use for then move to the systematic analysis of ceramic raw materials and their behavior in different phases of production. IDENTIFICATION AND CHARACTERIZATION CERAMIC RAW MATERIALS Many properties of clays and other ceramic raw materials depend the type and proportion of various minerals that make them up, so that Identification of these minerals is of fundamental importance. The solution This problem is complicated by the fact that rarely ceramic raw materials consist of pure and well crystallized minerals: generally, we with lots of minerals present in significant amounts and many other constituents in smaller quantities. In this case, can be very difficult identifying the main phases, especially if they are similar. Sometimes, it is often the case with clay, a mineral can not be identified if not carried out preventive cleansing and separation. On the other hand, same clay can contain different minerals and almost always is associated with important amounts of quartz, limestone materials, mica and other materials. Moreover, the clay minerals have particle sizes too small (the dimensions are common to 100 , ie 10-6 cm), which certainly not conducive to the identification, in addition, raw materials are clay often characterized by isomorphic substitutions, due to conditions genesis, as described in another chapter.

Therefore, in general, the analytical methods used to study of these materials premiums must be able to recognize the minerals that present a composition is not constant, which are often mixed each other, sometimes with tiny grains of dimensions. Since the identification of a mineral depends on its fundamental characteristics that must be necessarily always the same, regardless of the position and environment surrounding it, should employ analytical methods using properties the univocal individual classes of minerals. These can be summarized as follows: - The properties depend on the chemical nature of the mineral. - The aspect dependent mineral crystal. - The management dependent atomic or ionic crystal structure. - Those that rely on chemical or physical changes due to mineral the controlled alteration of the external parameters, ie p., the enthalpy changes by heating or cooling. Likewise, other known practical methods to identif identify or estimate in a about the presence of some minerals in raw material ceramics: for example, high values of the rheological properties as plasticity, thixotropy etc., may suggest the presence of certain minerals clay, like the magnetic properties can indicate the presence of ferromagnetic minerals, etc. These methods usually provide a picture features of the predominant mineral in the mixture, but are unable to solve the identification of individual components. The detailed description of the analytical methodologies that can be used for the recognition of the minerals in a ceramic material beyond of the objectives of this work, but it is certainly useful to indicate aspects most important of the main techniques and criteria that are based, as in the description of individual species, often also refer to data analytical features. Sampling A good analysis, in whatever form, running on a composite sample a mixture of base components, especially if it is homogeneous, requires First, a good sampling, which allows a small aliquot of material, necessary for analysis, representing all of the shows, sometimes consisting by several tons of material taken from the stockpile for the preparation of pasta a ceramic company: the analytical sample must therefore be representative of the total, and not a part of it. Based on the more general case, ie the ie the sampling in the quarry (for which and standardized procedures are in place), the sample must be taken from different parts of the extraction front, and at various depths, when the material seems to really even be able to select and retain, after quadripartition mixed and samples taken, a sample equivalent to about 1% of total but in the case of heterogeneous basic material, you must choose up to 5% of the sample, to obtain a reasonable sample for analysis. The same reasoning applies for samples taken from ships or articulated trucks loaded with bulk material. The preliminary sample selected in this way is homogenized then

to be submitted to quadripartition again, by training crushed and take lots opposite quarter, until a final sample 10-12 kg, which will be milled and subjected to quadrto quadripartition again until obtain a perfect sample of approximately 3 kg, with a mean grain size not superior to 0.5-2 mm, without excessive grinding, to prevent possible oxidation sensitive components in contact with air, for similar reasons, humidity contained in the sample should not be completely canceled during reduction size distribution and quadripartition, but must be between 4 and 12% for prevent tampering or loss of soluble salts. Drying and milling final made only just before analysis, and depending on the requirements of type same analysis. The type of particle size reduction, in turn, may result critical, both because of possible contamination by grinding media, especially if they are metal, such as the ability to profoundly alter the structure of some minerals (eg two-dimensional conformation). Chemical analysis The Potters are generally considered to be interesting to determine the type and proportion of each element in a sample, but these tests often have little meaning for themselves. The presence or absence of certain elements in certain proportions may in fact have a meaning in determining behavior in cooking, but rarely provide any information on the workability of the raw material (milling, spray drying, pressing, drying) and their physical behavior. Despite this, the elemental analysis, properly conducted, should be considered an exact science, while many other analytical techniques and determination technological properties are subject to errors and uncertainties; In addition, the combination of structural data with compositional data allows performing a semiquantitative identification of minerals present. Chemical analysis techniques are many, and modern instrumental techniques in particular allow fast and accurate results, where the accuracy the outcome is influenced mainly by the selection and preparation phase sample, always necessary to obtain homogenization complete. The results of chemical analysis of any substance is usually expressed oxides and ceramic materials for pulp in particular, are often 8 indicate main silicon dioxide (silica SiO2), aluminum trioxide (alumina Al2O3), titanium dioxide TiO2, iron trioxide, ferric oxide or Fe2O3 oxide Calcium CaO, MgO magnesium oxide, sodium oxide and potassium oxide Na2O K2O. Volatile oxides at 1000 C (oxide or carbon dioxide, CO2, CO, oxides of sulfur as SO3 and SO2, along with water) is usually given as loss by calcination. Rarely an accurate analysis can be closed at 100% to these components, since they are always present in quantities of other elements higher or lower, but still measurable by some fraction of percent, such as barium, strontium, transition metals such as copper, chromium, manganese, etc., boron, lithium, etc. As mentioned above, this type of analysis does not indicate the forms combination of different elements, and this can lead to errors technology assessment: consider the assessment of the calcium oxideum oxide from of a feldspar instead of limestone, or sulfur oxides that do not distinguish a

possible presence of sulfide minerals (pyrite, for example). Therefore, before starting a chemical analysis is necessary to select the sample accurately, using the methods described above, whose consistency varies typically from a few hundred milligrams to 1-2 grams after have carried out a careful drying at a temperature that does not alter the content volatile substances, and then passed to the mill to be conducted grinding media to ensure maximum performance without contaminating the sample. These methods vary depending on the hardness of the sample, moving from manual methods corundum mortar, or preferably natural agate up micromolinos with bodies grinding hard alloy appropriate. After weighing the sample (and this is the phase error that may result in more throughout the analysis), identify the method of attack itself, which allows the most complete homogenization, normally operated by dissolving sample in the appropriate chemical reagents, and obtaining a solution homogeneous liquid, or by the dissolution, in the molten state in a glass convenient to conduct a further analysis of this solid solution. Unfortunately however, ceramic materials, being based on silicates, aluminates and oxides, is quite difficult to solubilize, and in this respect There is an extensive bibliography that provides specific, as agents of attack hot liquid mixtures of hydrofluoric acid, HF, and other mineral acids, as nitric acid, HNO3, hydrochloric acid, HCl, or sulfuric acid, H2SO4, operating in containers appropriate. Chemical analysis "classic" by expected wet and complex treatment systematic samples, by separating the individual components before the actual analysis, carried out mainly by means of gravity (long and complex), colorimetric or complexometric (need to make every Preliminary calibrations precise time). These methodologies, but still today more than valid, have been clearly overcome by the development of techniques increasingly instrumental more sophisticated, which, on the sample promptly solubilized or even, as they allow the immediate collection analytical results. Obviously, all the determination is influenced primarily instrumental by the initial measurement of the mass of the sample and the correct preparation, which, whatever, should provide more standardized conditions and comprehensive as possible to homogeneity. The main methods of attack and acid stabilization of raw materials ceramic interest are: - Hot acid attack in open containers, using mixtures acid-oxidizing, based on HCl, HNO3 and HClO4: the need to decouple silicate matrix is almost always necessary as the use of HF, and at therefore unable to use normal glassware borosilicate glass. The use of ouse of open containers, together with a solubilizing acid high temperature may contribute to loss of volatile components. - Hot Acid attack in closed containers, and therefore also higher pressures. These systems are increasingly stretched by the speed of attack and the solution, usually make use of Teflon containers and systems programmable heating with microwaves. - Fusion alkaline and acid solubilization then usually HCl.

There is a wide range of alkaline fluxes, used in a function of temperature desired fusion and the efficiency of the process: in all cases, of course, There is the addition, through the flux of at least one cation, which is no longer true effectively quantify the unknown. More alkaline fluxes used are NaKCO3, NaOH, and Li2B4O7 LiBO2, with the addition of different salts that act as disintegrants (mainly lithium halide or alkaline general) complexes, etc., see table below. Melting temperature of the compounds used in the decomposition of material by melting.

(1) After the decomposition and transformation of bisulfate in pyrosulfate (K2S2O7) (2) Introduced bihidratada usually in the form; (3) As PbO after decomposition and release of carbon dioxide at 315 C; (4) As PbO after decomposition at about 500 C. The fusion can be performed manually or automatically, with the assurance standard operating conditions in any case in plat in platinum containers or the like, and glass can be obtained directly under the instrumental reading or be solubilized with precision, the solution for reading, then by appropriate dilutions. Whatever the instrumental technique used, it is obviously necessary preventive construction of different calibration curves, using standard solutions or solid in the range of reading course unknown samples. The main instrumental analytical methods used for chemical analysis quantitative analysis of ceramic materials based on feedback, emitter type fluorescence, absorption or emission of the sample with electromagnetic radiation; These are, therefore:

X-ray fluorescence (XRFnce (XRF) technique in which the minerals as such or, more finely dispersed in an alkaline glass is bombarded with radiation High frequency, low wavelength, which contains enough energy to induce a fluorescent emission due to excitation of internal electrons the orbits of the elements present, these electrons emitted by the sample collected by an appropriate detector, and the signal generated is associated with the position sample or the detector itself, establishing a relative intensity of signal contrasts with the pattern. With these methods are easily quantifiable elements of medium-high atomic weight to the lower limit of Na - F, and more Recently, considerable efforts have been made to obtain a determination also repeatable enough elements to boron (Figure 13). Atomic Absorption Spectroscopy (AAS-GFAAS), which uses energy absorption due to the presence of chemical species in atomic form, introduced in the path of one or more monochromatic radiation generated by appropriate lighting: in practice the test solution injected into a flame whose temperature, geometry and composition can ensure the presence elements in atomic form, and nonionic, and maximum interaction with incident radiation. For a better resolution is possible with some elements use as an energy source spray instead of a flame, heating rapid induction, within a tube made of graphite or other material appropriate, in a stream of inert gas. Under certain conditions, through this operating technique, you can also analyze a solid sample of easy volatilization. With these techniques it is possible to obtain optimal analytical results for all metal, to very low resolutions of the order, depending element of fractions of parts per million (Figure 14). Atomic Emismic Emission Spectroscopy (ICP-AES), a technique similar to above, however, where you use a subtractive rather than additive interaction of atomized element incident radiation. In this case, the sample solution is atomized by the combined action of high temperature of a standard torch applying a radio frequency source. The advantage over the systems absorption, is the possibility of sequential analysis of each sample without modify the source, the limit for registration of individual items is often worse, although some elements have better performance. In any case, it is possible down to a detection of p.p.m. or p.p.b. without major problems (Figure 15). Naturally, other methods of chemical analysis that can be selected particularly in relation to the pursuit of certain elements (one for all: the flame photometry to search for alkali elements), but for specific description we refer the reader to specialized texts. On the other hand, is undoubtedly important to note the option of selecting trials specific chemicals to verify the presence of certain elements (carbon, sulfur, fluorine, etc..) or anions (carbonate CO3 2 -, SO4 sulfate 2 -, etc.) Techniques usually simple and effective analytical, allowing assessments very important for the purposes of the applicability of a raw material for a process

ceramic.

Figures 13-13 th. Operating principle of instrumentation for chemical analysis by fluorescence X-ray (XRF).

Figure 14. Operating principle of instrumentation for atomic absorption spectroscopy (AAS).

Figure 15. Operating principle of instrumentation for atomic emission spectroscopy (ICP). Mineralogical analysis (or crystallographic) This type of research allows for the presence of single crystalline phases in a sample, tracing and, in its mineral composition, whose valuation is of fundamental importance for defining the technical characteristics raw material itself or its contribution to a paste. A preliminary form of the mineralogical data obtained by observation, First, the eye and then by microscopy, reflected light, polarized and transmitted (in a sample reduced to a thin a thin film after being stuffed resin): combining other optical properties like refractive index with those observations, it is possible, with the necessary scientific training rather simple specified, get a good discrimination and recognition. All science application of optical microscopy mineralogical investigations in materials ceramics is a branch of application singular, supported by numerous and technical publications, which have been broadcast between 1940 especially 1960. The technique may now be the main resolution mineralogical analysis is, without doubt, the X-ray diffraction (XRD), realizable on individual crystals or, more commonly, on the powders (Fig. 16). X radiation incident on a sample, appropriately filtered so as to obtain monochromaticity, interacts with the crystal lattice of the same, resulting diffraction configurations are correlated by the equation N = 2dsen Bragg, with distance d interreticular glass, depending on the angle diffraction. By selecting a wide range of X-ray sources, although the most spread is clearly one that can be obtained by anticathodes Cu, filtered Ni to issue only the Cu Ka = 1541 , it is appropriate to list each set of interactions of a given crystal lattice with the ratio of distances active grid, expressed in Angstrom (). For all crystalline substances are available indexes or databases data (PDF, see the examples in Tables 5 and 6), to be maintained and updated charge an international organization for recognizing the crystalline species in natural and synthetic samples and recently are being refining computer programs that allow modal data management

diffractometers, coming to provide quantitative assessments of the presence of individual minerals. Of course, operating on the powder, it is essential that the sample is very representative the whole, and not present at all orientations preferential crystals easily developed due to a two-way and for this reason, the preparation and processing of the sample assumes paramount importance. The grind should be as efficient as possible, avoiding the modification of the characteristics structural sample, especially if clay, to promote better standardization of all phases present and the random direction of all faces present clear, in fact, not wanting to proceed to the analysis by rotating sample holder, usually not available, we need to be reasonably sure have prepared a sample heavily disoriented, also the concomitant presence of phases of different density and crystallographic habit inopportune such as clays and mica materials, which have shaped micelles highly developed in two directions.

Figure 16. Photo left: Team X-ray diffractometer analysis, upper panel: working principle. The X-ray diffractometer analysis can be considered without more routine, with relatively simple and quick, and simple enough matrices allows interpretation of the data easily obtained, also allowing for Combining the proven presence of some crystalline phases, the allocation of its chemical formula "type" and, in combination with the quantitative chemical analysis, making the so-called rational analysis of a subject or a paste, ie make a approximation of the typical mineral composition expressed. In this way, example, a ceramic paste will be possible to assess not only their chemical composition oxides, but also its mineral composition, expressed in quartz, kaolinite, illite, calcite, dolomite, albite (sodium feldspar), microcline (potassium feldspar), ETC. see example in Figure 17. Thermal analysis As noted by the name in plural, the analysis can be out to verify the variation of the parameters in terms of an increase (or decreasedecrease) temperature is more than one. In fact, it is possible to record, depending a particular temperature gradient, changes in weight, temperature, heat developed or absorbed, dimensions, gaseous substances emitted, and so on., to each of These techniques shall be a type of analysis, which takes its name from the initials corresponding English words:

 TGA (ThermoGravimetricAnalysis) [TGA (thermogravimetric analysis)] DTA (DifferentialThermalAnalysis) [ATD (thermodifferential analysis)]

Table 5. PDF tab crystallographic data of quartz (SiO2).

Table 6. PDF tab crystallographic data of kaolinite. "Single firing porous, colored pasta" dry milling, pressing.

Figure 17. Example of tab-pasta, with rational analysis obtained from techniques XRF & XRD. DSC (DifferentialScanningCalorimetry) [CBD (differential scanning calorimetry)] TMA (ThermoMechanicalAnalysis) or DIL (Dilatometry) [ATM (analysis thermometer chanical) or DIL (dilatometry)] EGA (EvolvedGasAnalysis) [AGD (analysis of gases released)] These types of analysis, and represents an obvious way to observe and predict the behavior of a single material or a paste for drying, cooking or cooling, represent an aid for determining optimal mineralogical composition of a mixture, observing the different types of effects in close correlation with the crystal structure and transformations phase of the different minerals, and also represent a possible aid in determining the chemical, for example by allowing to recognize the presence of minerals and salts such as dolomite, carbonate, sulfates, sulfides, fluorides, etc. (Figures 18-22). The instruments used for thermal analysis consist mainly As one head, suitable for hosting the test sample in the right way and physical changes that transform electrical signals shown in zoomable manageable, and a heating system, usually based on resistance

Figure 18. Comparison of DTA curves more significant, conveniently schematized, clay minerals: A = kaolinite; metahalloysita B = C = montmorillonite-Na, D = montmorilloniteCa, E = vermiculite, sepiolite F = G = palygorskite.

Figure 19: Differential Thermal Analysis (source: G. Peco 1952).

C = kaolinite, Cr = cristobalite; H = halloysite, Q = quartz, I = illite, Ca = limestone; M = montmorillonite. TG analysis, PDD, ATD, ATE Hirschau on kaolin (source: E. Kaisersberg and C. Urso).

Figure 20. Examples of dilatometric curves of a crude sample, which undergoes transformations irreversible (curve a), and a sample already cooked, which, on cooling, runs substantially curve obtained on heating. power, which is due strong characteristics of stability, uniformity and programmability, thus ensuring perfect reproducibility of the measurements. It is often possible to combine some of these tests on a single computer, ATG + ATD example, or ATG + CBD, and ATD + AGE or ATG + ATD + AGE

so that, in a single step, to obtain a large amount of information. In order to describe briefly the working principle of some these teams, we can consider the most common applied to the ceramics sector namely the simultaneous analysis dilatometer and ATG + ATD. Dilatometric analysis to measure the expansion and contraction of a sample

Figure 21. Expansion-contraction (DC) and analysis Differential thermal (DTA) of secondary minerals (Source: G. Peco 1970). Ca = calcareous Q = Quartz, Cr = cristobalite, F = feldspar.

Figure 22. Expansion-contraction (DC) and Differential thermal analysis (DTA) of typical clay minerals (source: G. Peco 1970). C = kaolinite, H = halloysite, M = montmorillonite, Mi = mica.

preformed timely manner (usually in the form of a small parallelepiped or cylinder of 10 mm () x approximately 35-45, raw or cooked biscuit, indifferently), while offsetting the elongations of the system measurement and support, usually consisting of quartz, for tz, for measures to 950-1000 C, or alumina (up to 1350 C) for their known and modest expansion. It is clear that under the action of heat, clay substances in particular

but also all other materials, undergo expansion and contraction depending what happens inside, in particular the loss of the components volatiles, mostly water, induces a "collapse" of the crystal structure clays, which may manifest as a sharp contraction at temperatures characteristics. Thus, it may be possible to identify points Critics of a material and, depending on the temperature characteristic of values maximum contraction and intensity will be possible to identify and distinguish presence of zeolitic water, related to the presence of spaces interreticulares between the clay micelles sufficiently large chemical water is that hydroxyl formation of the primary lattice, transformations Structural yet (such as the important transition from -quartz - -quartz), the disappearance of reactive phases, etc. The curves obtained dilatometric some materials, present in figures 20, 21 and 22 are significantly representative of the possibility. There is also another important use of dilatometric curves obtained pastes and ceramic raw materials: the measure of the tendency of a material dilate or contract in a given temperature range, ie, its coefficient linear thermal expansion. This is expressed by the following relationship:

being the linear thermal exprmal expansion coefficient between T1 and T2, L0 is the length initial sample, L is the difference between LT1 and LT2, whereas in practice production is a consolidated approach using the coefficient of expansion cube obtained by multiplying by 3 the linear coefficient obtained from the dilatometric measurements, according to the arbitrary assumption that the trend dimensional variation is the same in all directions. This information is extremely important for assessing the desirability of coupling of different materials during heating and, especially, during cooling, which leads to permanently retain any tensions accumulated due to a lack of agreement dilatometric, this is a classic case of glazes applied over a fired ceramic bisque and then or at the same time with the support (figure 23). In light of the brief summary above, it is clear that there is a possibility or rather, the need to make a number of analytical tests "fine" on raw materials used in the ceramic process, the necessary instrumentation is not normally available to productive enterprises, so that the controls is normally provided by outside laboratories or entities capable of performing these accurate investigations. This does not mean that, within firms, not of great importance to organize a series of production controls, which allow work with continuity and consistency. The more frequent and accurate are these controls, the greater the control

Figure 23. Opposite effect because of the lack of coupling between the enamel and dilatometric support ceramic set by cooling: A case Enamel> cake - enamel case B <s

Figure 24. Dilatometric equipment.

production process, with the possibility to quickly correct errors or deviations adjustment, the more precise and tidy are the collection, interpretation and documentation of monitoring results, the easier it will resume after a particular product line, optimizing production in a short time. For these reasons, the following is a brief outline of key controls to be made. Plastic Raw Materials, Semi plastic and nonplastic Determination of the characteristics of the starting material. On materials base are determined: Humidity Aspect Residue Carbonates Reducing substances Expressed as% moisture Weigh a sample of wet material (Ph), dried to constant weight in a laboratory oven at 110 C for about 24 h and the sample is weighed dry (Ps). The difference between the 2 weighings divided by the weight of wet sample multiplied by 100 gives directly the moisture of the sample:

Appearance of the starting material Recorded the shape and dimensions (size) of the starting material and color and all other known characteristics. Residue on different screens It weighs 100 g of dry sample and treated in a laboratory shaker for 30 minutes with 300 ml of deionized water, added 1 g of tripolyphosphate sodium or sodium polyacrylate, until the particles are completely disrupted

and dispersed. Sieved sieves the slip in 1000, 2500 and 10,000 mallas/cm2 (180, 125 and 60 microns). Obtained are dried in several screens until constant weight and must be weighed. These values give directly the percentage of residue on different sieves. For non-plastic materials may be interesting to make a determination Dry, analyzing approximately 200 g of dried material on

Figure 25. Equipment for determination of different size fractions. a column of sieves with appropriate clearances of [p. eg. 11 (2000) 35 (1000) 140 (500) - 590 (250) - 1600 (150) - 4700 (90) and 9500 (63) mallas/cm2 (microns)].

Carbonate content in% of CaCO3 The determination was performed with a calcmetro (eg. Pizzarelli and Dietrich Frhling). A sample of one gram of dried material at 110 C, which should be introduced into a suitable container. In the container, a tap is inserted dilute hydrochloric acid (1:1). In the event that the material contains carbonates of any kind, it follows CO2, which, exerting a pressure proportional to the amount of carbonates, cause the decrease of the water column on the graduated cylinder which is read directly, or calculated, the percentage value of carbonates, CaCO3 as contained in the raw material. Knowing the volume of CO2 developed and the absolute temperature, the calculation is applied: % CO2 = 52146.2 VCO2 (L) / K Assuming that CO2 has been developed solely from CaCO3:% of CaCO3 =% CO2 2273. Determination of total reducing substances

Figure 26. Equipment for determination of carbonate minerals (calcite and dolomite).

Is effected by a lowering retrovaloracin oxide. It weighs about 2 grams of powder less than 200 microns, is transferred to a beaker of 400-500 ml, and adding 10 ml of a solution of K2Cr2O7 1 N (49 g one liter of distilled water) and 10 ml of concentrated H2SO4, shaking the container hand for approximately one minute, then letting it slowly digested with magnetic stirring for 30 minutes (the color should be a tone amarillonaranja: if green is added again 10 ml of dichromate). Then add 10 ml of 85% phosphoric acid, Complexed iron present, and diluted with distilled water to 200 - 250 ml, is added approximately 2 ml of indicator solution (0.16 g of barium difenilaminosolfonato in 100 ml of distilled water) and titrated with 0.5 N FeSO 4 (140 g in 200 ml of water + 40 ml distilled conc H2SO4., led to a liter, stored in a dark glass) with slow agitation, increasing color blue to green equivalent point clear. The value obtained must be corrected by the actual ratio of oxide reducer reagents (white), obtained performing the same test without the sample. Calculation: reduced K2Cr2O7 ml x 0.69 (factor estequiomtrico) / sample weight (g) = total% reducing substances Example: Test "white" additive K2Cr2O7 10.0 ml, FeSO4 needed for the steering without clay 21.5 ml: correction factor = 0.465 (10/21.5). Test Measurement: 2,125 g sample + 10 ml K2Cr2O7, FeSO4 necessary for 19.25 ml shift: 10 - (1925 x 0465) x 0.69 / 2125 = 0.34% reducing substances total. This measure provides mainly organic substances in the sample, but is influenced obviously also by the simultaneous presence of any reducing substance, and, in particular minerals such as sulfides pyrite, marcasite, etc..