DOI: 10.1002/adem.

200800019

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Synthesis and Properties of Porous Hybrid Materials containing Metallic Nanoparticles**

By Michaela Wilhelm*, Michael Adam, Marcus Bumer, and Georg Grathwohl
The pyrolysis of preceramic polymers like polysiloxanes provides the possibility of manufacturing ceramics at lower temperatures (5001500 C) compared to the powder sintering route and of using versatile polymer shaping routes, what has attracted a growing attention in the last decade.[1] Ceramic products with different structures and functions (e.g. bulk materials,[2] composites,[3] coatings[4] and foams[5]) were manufactured by this route and their properties (e.g. oxidation and thermal resistance,[6] electrical conductivity[7]) can be altered by tailoring the molecular structure of the precursor and by loading the polymer with filler particles.[8] The transformation of polysiloxanes [RSiO3/2] carrying hydrocarbon groups (R = methyl, phenyl, vinyl) in an inert atmosphere is well investigated and results in the formation of an amorphous silicon oxycarbide (SiOC, 8001000 C), which decomposes to a ceramic consisting of SiC, SiO2 and graphite at higher temperatures (14001500 C).[9-12] There are many examples, where a combination of a polysiloxane with a metal or a metal salt was used to prevent shrinkage, crack and pore formation of the resulting dense ceramic following the active filler controlled polymer pyrolysis concept (AFCOP).[2,13,14] Other groups used metal salts to introduce electrical conductivity or magnetic properties to SiOC materials[15] or investigated the Ni catalysed formation of carbon nanotubes in the resulting ceramics, which was observed applying temperatures beyond 800 C.[16] The size of Ni nanoparticles (< 1 wt.%) formed during pyrolysis from methylphenyl polysiloxanenickel acetate precursor came up with average diameters of 4060 nm. A partial conversion of polysiloxane precursors below 800 C yields novel hybrid materials, which often exhibit high porosities and are therefore considered to be potential materials for adsorption and for catalyst supports. However, an adjusted design or functional testing of these hybrid materials in terms of sorption behaviour or catalytic activity has only been performed in far cases.[17] The current study focuses on the use of Ni and Pt containing polysiloxanes for preparation of highly porous hybrid materials (so called ceramers) by inert gas pyrolysis (400 600 C) for use as adsorbent and as catalyst. In order to realize a homogeneous distribution of metallic particles at high metal contents 3-aminopropyltriethoxysilane was used for complexation of metal ions also in the combination with varying amounts of phenyltriethoxysilane. At the same time it was of interest how the different polarity of the siloxanes used for precursor preparation influenced the surface characteristic (hydrophilic/hydrophobic) of the resulting ceramers. These surface characteristics were examined in sorption experiments and first catalytic measurements revealed the catalytic activity of these ceramers. Experimental Synthesis of Polysiloxane Precursors and Processing of Ceramers For the synthesis of metal containing polysiloxane precursors 3-aminopropyltriethoxysilane (APT, ABCR) was added to a stirred solution of nickel acetate tetrahydrate (Ni, ChemPur GmbH) or hexachloro platinic acid (Pt, ChemPur GmbH) in ethanol resulting in complex formation. To prepare precursors containing additional phenyl groups, the addition of phenyltriethoxysilane (PhT, ABCR) followed. The components and their molar ratios are given in materials denotation. These silanes were cross-linked using a solution of NH4OH (2 N) as catalyst for hydrolysis-condensation reaction under reflux (Ni containing samples) or at room temperatures (Pt containing samples) for 3 days. After removing the solvent under reduced pressure, the precursors were dried (70 C, 24 h), ground and sieved. Powders with particle sizes smaller than 125 lm were used to press samples of 70 mm 5 mm 5 mm. Compacting was not possible in case of APT:Ni samples; these powders were directly pyrolysed. Finally, all samples were heat treated in a flowing atmosphere of nitrogen at 400, 500 and 600 C. For comparison, commercially available methyl (MK, Wacker Chemie GmbH) and methylphenyl polysiloxanes (H44, Wacker Chemie GmbH) were

[*] Dr. M. Wilhelm, M. Adam, Prof. G. Grathwohl Ceramic Materials and Components University of Bremen Am Biologischen Garten 2 / IW3, D-28359 Bremen, Germany E-mail: mwilhelm@uni-bremen.de Prof. M. Bumer Institute of Applied and Physical Chemistry University of Bremen Leobener Str., D-28359 Bremen, Germany [**] Financial support from the German Research foundation (DFG) and from the University of Bremen is gratefully acknowledged. The authors thank Oliver Oppermann/Prof. A. Rosenauer, University of Bremen, for the TEM characterisation.

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thermally cross-linked (200 C) and the cured materials were processed like described above.

0 -10

MK H44

Hybrid materials were analysed in terms of pyrolytic conversion by thermogravimetric analysis (TGA, (STA 503, Bhr)) in the temperature range of 25--1000 C. The development of porosity was examined by recording nitrogen adsorption isotherms at 196 C with an automated surface area and porosity analyser (Gemini 2375, Micromeritics). Furthermore, water and n-heptane adsorptiondesorption isotherms were obtained by volumetric vapor adsorption (BELSORP 18-3, Bel Japan, Inc.) at 22 C. Prior to sorption experiments, all samples were out gassed at 100 C under flowing nitrogen (24 h). Transmission electron microscopy (TEM, Philips CM20 UT) was used for the examination of distribution and size of the metallic nanoparticles. Finally, the catalytic activity of Pt containing ceramers for CO oxidation was measured in fixed bed reactor. For this purpose, powdered samples were mixed with quartz sand, placed on glass wool and purged with a continuous gas flow of 8.425 vol.-% CO in 91.575 vol.-% synthetic air (48.6 ml/min) at different temperatures up to 300 C. The conversion of CO was detected with a photometric detector (URAS G3, Hartmann und Braun). Prior to measurements, samples were treated in a flow of hydrogen (45 min, 300 C) to ensure complete reduction of metals.

Weight loss [%]

Microstructural and Functional Characterisation of Ceramers

-20 -30 -40 -50 -60 0 APT APT_Ni 1:1 APT_Pt 208:1 200 400 600 800 1000

Temperature [C]
Fig. 1. TGA thermograms of a methyl (MK), a methyl/phenyl (H44) and an aminopropyl (APT) polysiloxane as well as of aminopropyl polysiloxanes containing Ni(OOCCH3)2 (APT:Ni 1:1) or H2PtCl6 (APT:Pt 208:1) in the given molar ratio under nitrogen atmosphere.

Results and Discussion Pyrolytic Conversion of Polysiloxane Precursors

differed markedly, although the calculated content of organic groups of cured H44 (51.5 %) and APT (52.7 %) is nearly the same, indicating that the remaining carbon content in APT calculated from weight loss in the temperature range of 360 1000 C amounts to just 15.7 %, what is half of that of H44 (28.7 %). The weight loss of APT:Ni 1:1 is characterized by the additional degradation of acetate anions starting at 230 C, which is completed at 400 C confirmed by IR spectroscopy. In contrast to APT:Ni 1:1, where the decomposition of APT is not significantly influenced by the presence of the metal, the ceramic yield of APT:Pt 208:1 is somewhat higher than for pristine APT, indicating a higher amount of organic groups converted to amorphous carbon probably due to Pt catalysis.

During heat treatment of polysiloxane precursors in a niEvolution of Porosity in Ceramers trogen atmosphere a loss of weight generally occurs due to [9] The decomposition of organic groups accompanied by different conversion reactions At temperatures below evaporation of gaseous compounds during pyrolysis of poly250 C the evaporation of mainly water and solvent is obsiloxanes causes the evolution of microporosity particularly served, which are released while cross-linking of siloxanes is in the temperature range between 400600 C. Figures 2 a/b accomplished. At higher temperatures the organic groups of reveal that the highest surface areas for all investigated matethe precursors start to decompose under formation of hydrorials were found after pyrolysis at 500 C reaching up to gen, volatile hydrocarbons and of amorphous carbon remaining in the matrix. The thermogravimetric analysis of commercially 700 700 available methyl (MK) and methylPhT:APT:Pt 165:4.7:1 a APT b APT:Ni 6:1 600 600 phenyl polysiloxanes (H44) in comAPT:Ni 1:1 APT:Pt 208:1 parison to polysiloxanes based on 500 500 APT demonstrated that the thermal 400 400 stability of aminopropyl chains is 300 300 lower (Fig. 1). 200 200 While the onset of significant dePhT:APT:Ni 80:10:10 PhT:APT:Ni 66:17:17 100 100 composition of MK and H44 was PhT:APT:Ni 44:28:28 PhT:APT:Ni 24:38:38 0 0 found at temperatures of 550 and PhT:APT:Ni 10:45:45 420 C, respectively, a massive weight 400 500 600 400 500 600 Pyrolysis temperature [C] Pyrolysis temperature [C] loss started at 360 C in case of APT. Fig. 2. Specific surface area of hybrid materials derived from pristine and metal modified aminopropyl polysiloxanes (a) Furthermore, the ceramic yield of and from polysiloxanes containing phenyl and aminopropyl groups as well as Ni or Pt salts in different molar ratio (b) in H44 (73 %) and APT (58 %) at 1000 C the temperature range of 400600 C under an atmosphere of nitrogen.
Specific surface area [m /g]
Specific surface area [m /g]
2

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Wilhelm et al./Synthesis and Properties of Porous Hybrid Materials containing Metallic Nanoparticles 600 m2/g and that surface areas decreased with increasing amount of Ni or APT:Ni content. Therefore, a rising porosity due to the decomposition of acetate ions could not be detected. At temperatures higher than 500 C the pores started to collapse by viscous flow and as a result specific surface areas diminished. Although the metal content in APT:Pt 208:1 is very small the initial formation of pores is obviously inhibited here, resulting in a maximum surface area of only 100 m2/g at 500 C (Fig. 2a). Taking into account the lower weight loss observed for APT:Pt 208:1 compared to APT this finding supports the assumption of an Pt catalysed conversion of organic groups to amorphous carbon released as gaseous species for APT or APT:Ni 1:1. Sorption Properties of Ceramers To investigate the surface characteristic of metal free and metal containing ceramers sorption isotherms were recorded at 22 C using non-polar n-heptane and polar water vapour (Fig. 3a/b). In order to show general differences of ceramers and common adsorbents, the sorption behaviour of a mesoporous activated carbon, which was commercially designed for hydrocarbon adsorption (honeycomb, Westvaco Corp) is compared to that of a mesoporous bulk ceramer based on methyl (M120/MK600) and microporous ceramer foam derived from methylphenyl polysiloxanes (H44), the preparation process of which is described elsewhere.[17] These hybrid materials exhibit an n-heptane uptake at p/p0 = 1 in the range of 1224%, which depend mainly on the total pore volume and is comparable to that of activated carbon (18.9 %). However, the amount of water adsorbed by these adsorbents is completely different. While the water adsorption of the activated carbon reached 14 % due to capillary condensation in mesopores expressed by a type V isotherm,[18] the water uptake of both ceramers was negligible (< 0.6 %), indicating an outstanding hydrophobic nature of surfaces in ceramers. In contrast to that, APT and APT:Ni 1:1 showed a strong decrease in n-heptane adsorption (3.3 % and 5.6 %) and an enhanced water adsorption of 5.0 % and 6.3 %, respectively. This behaviour demonstrates the more hydrophilic surface

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characteristic of these ceramers, which could be explained by the incorporation of polar N atoms of decomposed aminopropyl groups in regions of amorphous carbon during conversion of precursors. Such incorporation of N atoms in the ring system of graphene layers is well known for activated carbon obtained by pyrolytic conversion of nitrogen containing polymers (e.g. polyarcylonitrile, polyimide) and leads to higher basicity of surfaces.[19] According to that and due to the higher retention of organic groups during pyrolysis of APT:Pt 208:1, the resulting ceramer exhibited a rather hydrophilic surface with a water uptake of 8.3% and a n-heptane adsorption of 1,8% (not shown in Fig. 3a/b). This incorporation of polar hetero atoms in the carboneous phase seems to be even more pronounced in the present of Si-bound phenyl groups. This assumption is based on the result that increasing the amount of APT and Ni salt in PhT:APT:Ni precursors from molar ratio of 80:10:10 to 10:45:45 induced a decrease in n-heptane adsorption (from 17.8 to 3.6 %) and an enhanced water uptake (from 3.6 to 10.2 %) (Fig. 4). The presence of metallic particles may also alter the surface properties. Considering the weight loss during pyrolysis at 500 C, the metal content was calculated to range from 5.2 % (PhT:APT:Ni 80:10:10) to 31.5 % (PhT:APT:Ni 10:45:45) for ceramers containing phenyl groups and to be 35.2 % in APT:Ni 1:1. Therefore the combination of silanes with non-polar and polar organic groups open up the possibility of fine-tuning the surface properties of resulting ceramers, what is important for adjusting materials to particular separation problems or catalytic reactions. Metallic Nanoparticles in Ceramers

The formation of metallic particles in polysiloxane derived hybrid materials was investigated by taking TEM images of the cured polysiloxanes and pyrolysed ceramers. For Pt-containing materials the measurements revealed that the initial generation of spherical particles took already place during the cross-linking/drying step, while no particles were formed in Ni-containing polysiloxanes under these conditions. Due to the higher reduction potential of Pt(IV) compared to Ni(II), the reduction of Pt(IV) cations was already accomplished by the complexa activated carbon (honeycomb) b ing aminopropyl group, the catalyst activated carbon (honeycomb) 404 m /g 25 25 M120XB/MK600 120XB/MK600 561 m /g H44 (NH4OH) and/or the solvent (ethaH44 654 m /g APT 20 20 nol). In cured APT:Pt 208:1 the Pt parAPT 519 m /g APT:Ni 1:1 APT:Ni 1:1 341 m /g ticles showed a spherical shape with 15 15 small diameters between 46 nm, 10 10 which were homogeneously distributed throughout the polymer. During 5 5 pyrolysis even at 600 C the particle size was retained, indicating a re0 0 0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0 markably stable embedding of partiP/P P/P cles in the ceramer matrix, preventing Fig. 3. N-heptane (a) and water isotherms (b) at 22 C of ceramers derived from different polysiloxanes by pyrolytic conparticle growth or sintering. In case version at 500 C in comparison to the isotherms of an activated carbon (adsorption and desorption branches are repreof polysiloxanes containing Ni ions, sented by filled and open symbols, respectively).
2 2 2

Sorption of n-heptane [%]

Sorption of water [%]

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20 18 Adsorption capacity at 22 C [%] 16 14 12 10 8 6 4 2 0 80:10:10 66:17:17 44:28:28 24:38:38

n-heptane water

diffusion of metal and the sintering of nanoparticles during preparation of ceramers is suppressed. The varying size of Pt nanoparticles in ceramers could be explained by the higher molar ratio of APT: metal salt enhancing the Pt reduction and thereby the particle growth, what was already observed in Pt:APT:TEOS system[20]. Furthermore, the diffusion of metal and sintering of nanoparticles is suppressed by the presence of phenylsiloxanes. The latter should be particularly attributed to the formation of Ni nanoparticles due the similar ratio of APT: metal salt in these samples. Catalytic Properties

10:45:45

Molar ratio of PhT : APT : Ni

Fig. 4. Maximum loading with n-heptane and water at 22 C of PhT:APT:Ni ceramers with different molar ratio of compounds derived by pyrolytic conversion at 500 C.

the reduction took place at higher temperatures due to reaction with decomposing organic groups[16] and lead in APT:Ni 1:1 and 4:1 ceramers to separated spherical particles with a broader distribution of particles size in the range of 4060 nm (1:1) and particle sizes around 50 nm (4:1), respectively. The bigger particle size compared to Pt particles in APT:Pt 208: 1 can be referred to the higher metal content in APT:Ni 1:1 and APT:Ni 4:1, which accounts for 35.2 or 16.3 wt.% compared to only 1.3 wt.% in APT:Pt 208:1 after pyrolysis at 500 C. At a lower Ni content of 11.7 wt.% in APT:Ni 6:1 smaller particles (2030 nm) were observed, but these particles were agglomerated to aggregates of around 150 nm in diameter. The dilution of precursors with additional phenyl siloxanes in PhT:APT:Pt 165:4.7:1 (Pt: 3.7 %, 24 nm) and PhT:APT:Ni 80:10:10 (Ni: 31.5 wt.%, 3545 nm) to PhT:APT:Ni 10:45:45 (Ni: 5.2%, 1520 nm) ceramers resulted in the formation of smaller nanoparticles and a close particle size distribution (Fig. 5 a/b) although the metal content of ceramers is comparable to that of APT:Ni or APT:Pt ceramers. In spite of a very small Ni amount (<1 %) and the use of an oligomeric methylphenyl siloxanes (H44), Scheffler et al. found a particle size of 4060 nm in the resulting ceramer,[16] indicating a more effective separation of metal ions by complexation with APT and by monomeric PhT used in this work. Therefore, the

In order to examine the catalytic activity and accessibility of the nanoparticles for gas molecules, first catalytic measurements using Pt-containing ceramers were performed. APT:Pt 208:1 (Pt: 1,3 wt.%) and PhT:APT:Pt (Pt: 3.7 wt.%) were tested with respect to oxidation of CO at different temperatures. Prior to these measurements, it was confirmed that no oxidation of the ceramer matrix (without metallic particles) occurred under measurements conditions. Fig. 6 shows the conversion of CO (open symbols) and the turnover frequencies (TOF, filled symbols), which represents the number of molecules converted per one surface atom of Pt particles and per time unit.[21] CO conversion over both ceramers started at temperatures around 200 C. In case of PhT:APT:Pt 167:4.7:1 sample, however, the conversion sharply increases at this temperature reaching already 100 %. Also, the obtained TOF (5.6) is significantly higher under these conditions as compared to APT:Pt 208:1 sample, clearly pointing to a higher catalytic activity of the PhT modified ceramer. For APT:Pt 208:1 sample, on the other hand, the conversion slowly increased with increasing temperature and reached 100 % (TOF: 23.1) only at 300 C. To reach a TOF which is comparable to the PhT:APT:Pt sample at 200 C, a temperature of about 280 C is needed. Recent studies showed that on Pt/SiO2 catalysts the CO oxidation is structure sensitive as the turnover frequency (TOF) increases with increasing parti-

30 100

PhT:APT:Pt 165:4.7:1 APT:Pt 208:1

28 26 24 22 20 18

80

Conversion CO [%]

60

16 14 12

TOF [s ]

40

-1

10 8 6

20

4 2 0

0 100 150 200 250 300

Temperature [C]
Fig. 5. TEM micrographs of ceramers PhT:APT:Ni 10:45:45 (a) and PhT:APT:Pt 165:4.7:1 (b) after pyrolysis at 500 C. Fig. 6. Conversion of CO to CO2 at different reaction temperatures catalysed by ceramers containing Pt nanoparticles.

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Wilhelm et al./Synthesis and Properties of Porous Hybrid Materials containing Metallic Nanoparticles cle size[22] and that 1% Pt/ZrO2 catalysts exhibit TOF values in a broad range between 11000.[23] These results demonstrate clearly that metallic nanoparticles in porous ceramers can be reached by the reactant and that these particles exhibit a promising catalytic activity. Future work should also confirm the catalytic activity of Ni nanoparticles in ceramers using appropriate reactions like the hydrogenation of alkenes. Conclusion Highly microporous hybrid materials with embedded Ni or Pt nanoparticles (135 wt.%) were prepared by inert gas pyrolysis of polysiloxane precursors containing polar and/or non-polar organic groups in combination with a metal salt. During heat treatment surface areas up to 600 m2/g developed, while surface polarity could be altered by varying the amount of polar aminopropyl groups in the precursors. The incorporation of N atoms of APT in the matrix of hybrid materials during pyrolysis enhanced the hydrophilicity of ceramers resulting in water uptakes up to 10 %, while an outstanding hydrophobicity with n-heptane loadings of up to 22 % was observed for ceramers derived from methyl or methylphenyl siloxanes. Metallic particles were found to be homogeneously distributed throughout the matrix showing rather small particles sizes of 1520 nm (Ni) and 24 nm (Pt), respectively, in case of PhT:APT ceramers. The particles size decreased with decreasing metal content in APT ceramers and in the presence of PhT in the precursor. As a result of first catalytic measurements performed with Pt containing ceramers it was shown that metallic nanoparticles are accessible for gaseous substrates and show good catalytic activity in CO oxidation. Due to the advantage of tunable surface properties and particles sizes, these highly porous, metal containing ceramers derived from polysiloxanes are promising materials for use as adsorbents and as catalyst adjustable to particular requirements of selective oxidation or hydrogenation reactions.

[1] R. Riedel, G. Mera, R. Hauser, A. Klonczynski, J. Ceram. Soc. Jap. 2006, 114, 425. [2] R. Harshe, C. Balan, R. Riedel, J. Europ. Ceram. Soc. 2004, 24, 3471. [3] A. Herzog, M. Thnemann, U Vogta, O. Beffort, J. Europ. Ceram. Soc. 2005, 25, 187. [4] J. D. Torrey, R. K. Bordia, Ch. H. Henager Jr., Y. Blum, Y. Shin, W. D. Samuels, J. Mater. Sci. 2006, 41, 4617. [5] P. Colombo, J. R. Hellmann, Mat. Res. Innovat. 2002, 6, 260. [6] F. I. Hurwitz, M. A. B. Meador, J. SolGel Sci. Technol. 1999, 14, 75. [7] J. Cordelair, P. Greil, J. Europ. Ceram. Soc. 2000, 20, 1947. [8] P. Greil, Adv. Eng. Mater. 2000, 6, 347. [9] C. G. Pantano, A. K. Singh, H. Zhang, J. Sol-Gel Sci. Technol. 1999, 14, 7. [10] P. H. Mutin, J. Sol-Gel Sci. Technol. 1999, 14, 27. [11] V. Gualandris, D. Hourlier-Bahloul, F. Barbonneau, J. Sol-Gel Sci. Technol. 1999, 14, 39. [12] G. D. Soraru, L. Pedeiva, J. Latournerie. R. Raj, J. Am. Ceram. Soc. 2002, 85, 2181. [13] P. Greil, J. Eur. Ceram. Soc. 1998, 18, 1905. [14] T. Michalet, M. Parlier, F. Beclin, R. Duclos, J. Crampon, J. Eur. Ceram. Soc. 2002, 22, 143. [15] P. Colombo, T. Gambaryan-Roisman, M. Scheffler, P. Buhler, P. Greil, J. Am. Ceram. Soc. 2001, 84, 2265. [16] M. Scheffler, P. Greil, A. Berger, E. Pippel, J. Woltersdorf, Mat. Chem. Phys. 2004, 84, 131. [17] M. Wilhelm, C. Soltmann, D. Koch, G. Grathwohl, J. Europ. Ceram. Soc. 2005, 25, 271. [18] K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pierotti, J. Rouquerol, T. Siemienewska, Pure Appl. Chem. 1985, 57, 603. [19] J. Machnikowski, B. Grzyb, H. Machnikowska, J. V. Weber, Microporous and Mesoporous Mater. 2005, 82, 113. [20] Ch. Lembacher, U. Schubert, New J. Chem. 1998, 25, 721. [21] M. Boudart, in: Handbook of Heterogeneous Catalysis, (Eds.: G. Ertl, H. Knzinger. J. Weitkamp), Verlag Chemie, Weinheim 1997, 3, 958. [22] F. J. Gracia, L. Bollmann, E. E. Wolf, J. T. Miller, A. J. Kropf, J. Catal. 2003, 220, 382. [23] A. Wootsch, C. Descome, S. Rousselet, D. Duprez, C. Templier, J. Appl. Surf. Sci. 2006, 253, 1310.

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