Journalof Sol-GelScienceand Technology8, 443-449 (1997) 9 1997KluwerAcademicPublishers. Manufacturedin The Netherlands.

Sol-Gel Coatings on Metals

MASSIMO GUGLIELMI Dipartimento di lngegneria Meccanica, Settore Materiali, Universit?t di Padova, Via Marzolo 9, 35131 Padova, Italy

Abstract. Sol-gel derived films can be deposited on metals to improve their resistance to oxidation and corrosion or to modify their surface properties. However, practical applications are limited by problems intrinsic to sol-gel processing or specific of coating/metal systems. Coatings aimed to improve oxidation and wet corrosion resistance have been the most studied. The results published in the literature Show that sol-gel coatings may offer good protection against oxidation. More difficult is to achieve a protection against wet corrosion. An important aspect of the application of the sol-gel method for coating metallic objects is also the deposition technique. Keywords: coatings, protection of metals, oxidation, corrosion

1.

Introduction

Ceramics are, in general, more resistant than metals to oxidation, corrosion, erosion and wear, and have good thermal and electrical properties that make them particularly interesting as coating materials. Ceramic coatings are usually deposited on metals for improving their performances in high temperature aggressive environments [1]. Some important applications are: improving resistance against gas-, solid-, condensed-, and molten-phase corrosion, to localized overheating and melting; decreasing fretting and wear; decreasing heat losses and/or reflecting radiations in high temperature systems. Low temperature applications are also important, where the coatings are asked to provide corrosion- and abrasion-resistance (for example, in the chemical industry) or good dielectric properties (for example for electronic packaging). There are several techniques for coating metals with ceramic layers: PVD, CVD, Plasma spraying, Electrophoresis, Sol-Gel. The deposition of sol-gel coatings on metals is relatively recent and has been not sufficiently investigated, in spite of its potential technological interest. Many

aspects remain to be clarified and a number of questions still wait for an answer. For a technological development of sol-gel in this specific field it would be important to understand at what level, and for which kind of applications, the method could be competitive with other more traditional techniques. A critical examination of the limits of sol-gel processing should help to indicate the most reasonable and promising fields of application and in which directions research efforts should concentrate. 2. Sol-Gel Coatings on Metals

Examining the published papers where sol-gel coating/metal systems have been produced and/or tested (see Table 1 for a concise picture), it can be seen that the studies were mainly aimed to test the capability of sol-gel coatings to improve oxidation and corrosion resistance of the substrate. So, these two main topics will be reviewed in more detail. Other examples of applications have, however, been reported. Stainless steel was made more repellent to water by fluorine-doped zirconia coatings [2]. Ormosil coatings were suggested as adhesion promoters [3]. The

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planarization of rough surfaces has been exploited, for example, by Ashley and Reed for application to solar mirrors [4]. Hard ceramic coatings could improve the resistance of metals to wear. However, only few reports have been published on microhardness, scratch or abrasion resistance of sol-gel coatings on metals [5-7] and more specific investigations are necessary to define the limits of sol-gel applicability in this field. Ceramic coatings may be considered for electric insulation. Brinker et al. produced silica films having quite high breakdown strengths (up to 600 MV m -1) and insulating properties approaching those of thermally grown silica [8]. Good ormocers for dielectric applications were reported by Schmidt and Wolter [9].
Table 1.

2.1. Protection Against Gas Corrosion The most common type of gas corrosion is oxidation. Oxidation of metals is a complex process which depends on the defect structure of growing oxides. In general, the oxidation rate of most common metals and alloys follow three kinetic laws: parabolic, linear, and logarithmic [10]. The parabolic law describes an oxidation process where ionic diffusion is the prevalent mechanism. It is followed by many metals at high temperature. The logarithmic law can often be used to describe the behavior at low temperatures, while the linear rate law is found when films or scales are nonprotective or may follow parabolic kinetics when microcracking or porosity develops in the film.

Sol-gel substrate/coating systems, Coating ZrO2 Study on Oxidation [12-15]; adhesion [16]; corrosion [14, 16, 25, 26, 28]; electrophoretic deposition [32]; interface [33] Wettability [2] Oxidation [5]; corrosion [5, 20, 25, 32]; scratch resistance [5]; interface [34]; electrophoretic deposition [35]; surface planarization [4] Corrosion [25] Corrosion [25] Adhesion [5, 36] Oxidation [17]; interface [34] Oxidation [37] Oxidation [16, 18] Corrosion [38] Adhesion [3] Oxidation [13] Oxidation [6] Oxidation [6, 21, 22]; corrosion [29, 38, 30] Electrophoretic deposition [39] Corrosion [38] Dielectric prop. [9]; corrosion [9, 31] Corrosion [40] Oxidation [6]; scratch res. [6] Adhesion [41] Oxidation [6] Corrosion [38] Oxidation and sulfidation [19] Oxidation [21, 22] Oxidation and sulfidation [19] Oxidation [42] Interface [34]

Substrate Stainless steel

F-doped ZrO2 SiO2

SiO2-TiO2 SIO2-A1203 Ormo-SiO2 Mild steel SiO2 SIO2-A1203 SIO2-B203 Binary silicates Ormo-SiO2 ZrO2 SIO2-B203 SiO2 Aluminoborosilicate Binary silicates Ormo-SiO2 Ormo-ZrOz Cu Ni Ni-based alloys Ag Co-based alloys Ti3A1 Ti SIO2-B203 Ormo-SiO2 SiO2, TiO2, ZrO2, SIO2-B203 SiO2, binary silicates SIO2-A1203 SiO2 SIO2-A1203 Aluminosilicate, borosilicate SiO2

Iron A1

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Ceramic coatings can protect the substrate from oxidation acting as barriers for the diffusing species (metal ions or oxygen) or may act as a source for reactive elements able to improve the oxidation resistance of the substrate [11]. Almost all the papers published in the sol-gel literature deal with barrier layers. Zirconia and silica coatings have been the most investigated. Zirconia is a well known solid electrolyte which transports oxygen ions at high temperature, so it is not, in principle, the best material for a barrier against oxidation. However, it has the advantage to have a thermal expansion coefficient close to that of stainless steel. Amorphous silica is a much better barrier to oxygen diffusion, but its thermal expansion coefficient is much lower than any metal. Both ZrO2 and SiO2 coatings deposited on stainless steel were shown to substantially increase the oxidation resistance at temperatures ranging from 650 to 950~ [5, 12-15]. The kinetics data, when reported, seems to follow a parabolic law, with rate constants reduced with respect to bare substrates. Increasing the coating thickness generally increases the protection effect, but with exceptions, as discussed below. Miyazawa et al. [15] reported that the oxidation rate of stainless steel coated with ZrO2-Y203 layers decreased with increasing Y203 content. They suggested that the effect could be explained by trapping of oxygen by yttria, or by diffusion of yttrium, known to be a reactive element for chromia scale-forming steels, into the substrate. Silica and borosilicate coatings have been deposited on mild steel from aqueous amine solutions [16--18]. These are more stable and less expensive than alkoxide solutions, and offer an interesting alternative. A notable protection was observed up to 750~ for both type of coatings. Their effect of B203 content was investigated. It was negligible at low temperatures, but increased with T. The minimum in the oxidation rate was found at B203 contents decreasing with increasing temperature. This can be explained by the important lowering of Tg with increasing B203 contents in the binary SIO2-B203 system, which makes stress relaxation and densification possible at lower and lower temperatures and avoids crack formation. At higher boron contents the viscosity becomes very low and the protective effect decreases. An evident improvement of oxidation resistance of nickel at 800~ was obtained with borosilicate coatings [6]. Good results were also achieved on Ni- and Co-based alloys by Williams and Interrante, using

specifically synthesized aluminosiloxane oligomers to deposit aluminosilicate coatings [19]. A field where sol-gel may be applied with success is the protection of front-surface metal mirrors for solar energy applications. Reed and Ashley used silica sols to fabricate a multilayer system [4, 20]: a first planarizing SiO2 layer on stainless steel, a silver layer deposited by sputtering and a silica overcoat. However, a degradation of optical properties was observed when the overcoat was deposited directly on the silver surface. A primary protective silica film sputter deposited prior to the sol-gel application was necessary to minimize this problem. More recent experiments performed by Morales and Duran [21, 22] show that very good results are possible using sol-gel silica layer directly on silver-coated stainless steel. A solar average reflectance of 0.95 was obtained, which is comparable with that of the best commercial mirrors used in solar applications. In addition, the silica-coated silver mirror exhibited excellent thermal stability up to 300~ and good mechanical properties. In most cases coatings act as barriers to diffusion, lowering the oxidation rate of the substrate. Therefore, thicker layers should offer better protection, in general agreement with experiments. However, it is found that when thickness exceed a certain value the behavior reverses (see, for example, Ref. [6]). This is certainly due to cracking of the coating, that occurs above a critical thickness. The increase in the oxidation rate due to cracks is likely to be proportional to the area of the unprotected substrate surface. Thus, the presence of tiny and localized cracks should not change too much the overall protection offered by the layer. Instead, this should dramatically decrease when extensive cracking and delamination is present in the film or occurs during exposure to high temperature. In some cases, homogeneous oxidation of the metal, without apparent damage of the coating, was observed [6]. This is likely due to the porosity of the film. This is not a great problem, as the porosity can be controlled, in some extent, through the chemical and processing parameters of deposition. Metals can be subjected to other forms of gas corrosion, but the only detailed experimental results were published by De Sanctis et al. [23], which tested silica-coated stainless steel in hot ammonia atmosphere. Compared to uncoated specimens, the coated ones showed substantially higher resistance. A single layer, 200 nm thick, exhibited localized attacked areas only after 115 h at 500~ The cross-section of

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the sample showed clearly that the attack grew radially from localized points on the surface, probably small discontinuities in the layer. Multilayers behaved worse, suggesting an higher concentration of defects in the coating. Significant inhibition of high temperature sulfidation by aluminosilicate coatings on Co-based alloys have been also reported [19].

2.2.

Protection Against Wet Corrosion

Reduction of wet corrosion rate at low temperatures, joined to improved wear resistance, would be of extreme practical interest. For this reason, the protective properties of sol-gel coatings have been investigated in corrosive aqueous media by several groups. Shane and Mecarteney [24] reported that zirconia coatings deposited on 446 stainless steel were able to protect the substrate from corrosion when a drop ofconcentrated hydrochloric acid was deposited on the sample. The behavior of zirconia-coated stainless steel (sonocatalyzed sols and heat treatment at 400~ for 1 h) in acidic solutions was investigated also by Atik and Aegerter [14] using 15% H2SO4aqueous solution at 81 ~ A sample coated with a film thinner than 40 nm did not show any chemical attack (measured by the weight loss) up to 24 h. Instead, a slightly thicker coating (55 nm) started to corrode after 10 h. From electrochemical measurements performed on the same type of samples, but withthicker coatings (0.3-0.6/zm) heat treated 2 h at 800~ it was found that the coatings were very protective against acid corrosion [25]. The results obtained in a further study [26] with 0.5/zm thick ZrO2 films showed that in aqueous NaC1 solutions the corrosion potential shifted towards more noble values by up to 300 mV and the corrosion current dropped, in one case, by a factor 17. Bad results were instead obtained with thicker layers. Thus, it appears that zirconia coatings are very protective against wet corrosion and there exist a critical thickness above which the protection decreases. However, from the above cited papers it is not clear if the estimated corrosion rate may be expected to remain constantly low also for prolonged times. This is, of course, an important aspect for practical applications. Electrochemical measurements were performed at different times during a 200 h experiment by Damborenea et al. [27] on silica-coated stainless steel. In this very recent study it was shown that in a HC1

solution with pH of 0.58 the polarization resistance of the coated samples was, at the beginning, much higher than that of the uncoated ones (more than 30 times), but it decreased with time reaching their value after about 30 h. As the polarization resistance is inversely proportional to the corrosion rate, it means that the coating is effective, but only for a relatively short period of time. This was explained by assuming an attack of the substrate through discontinuities in the film, which put the metal surface into contact with the aggressive medium, producing high current densities and accelerating the corrosion process. Such discontinuities may be cracks or pores. Differently from oxidation, where tiny cracks are not critical, the presence of even very small defects in the coating may have dramatic effects in a wet corrosive environment. Local breakdown of protective coatings at isolated sites cause a localized attack known as pitting corrosion. This is an insidious type of corrosion as it often remains undetected until failure occurs [10]. Chino et al. [28] determined the pitting corrosion resistance of ZrO2 coatings on stainless steel from potentiokinetic measurements. The test was performed in a NaC1 solution. The pitting potential of stainless steel (300 mV/SCE) was increased, after being coated with a 25 nm thick zirconia layer up to 700 mV/SCE. These authors compared coatings deposited from solutions of zirconium n-butoxide chelated by acetylacetone (acacH) and from solutions without acacH. Only the first type of sols gave coatings with good protective behavior, and this was attributed to their lower porosity. De Sanctis et al. [5] observed that stainless steel was much more resistant to the attack of a boiling 65% nitric acid solution when a silica layer was deposited after heat-treatment of the substrate at 650~ It was supposed that the precipitation of chromium carbide crystals, occurring during thermal treatment, could be the responsible for cracking of the coating. In fact, this was avoided by depositing tlae film on previously heattreated samples obtaining a much better resistance. Kato deposited silica multilayers on aluminum plates, using solutions without any catalysts, in particular without acids in order to avoid the attack of the metal by the coating solution [29, 30]. Measuring the corrosion resistance by an accelerated salt spray test, he found that the protection increased by increasing the number of layers. Increase of thickness by the multilayer technique reduces the probability of cracking. In fact, a total thickness of 1/xm (obtained with 20 layers) could be achieved, without apparent damage of the coating.

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Crackability of coatings can be avoided with organic-inorganic hybrid coatings. If the working temperature is not too high (less than 250-300~ organically modified layers may be, indeed, interesting candidates for protection of metals, because they may have higher thermal resistance and better mechanical properties than common polymer coatings. Kasemann and Schmidt reported that aluminum and magnesium coated with a nanocomposite material could resist at least one month of salt spray test and were stable against filiform corrosion produced by concentrated HC1 or prolonged permanence in saturated water vapor atmosphere at 40~ [31]. 3. Limits of Sol-Gel Application to Coating of Metals

Major drawbacks of sol-gel processing for coating metals are: crackability, thickness limits, difficulty to coatcomplex shapes. Sometimes also the thermal treatment may be critical. Cracks may affect several properties and may be deleterious in wet corrosive media, as previously discussed. They are due to stresses developing during drying and thermal treatment. Stresses in sol-gel derived films are due to shrinkage and thermal expansion mismatches. Tensile stresses develop during drying, and can lead to crack formation if the film is thicker than a critical value [43]. Experimental observations [44] are in good agreement with the model of Hu and Evans [45] in which film cracking occurs together with limited delamination at the film-substrate interface. Due to the brittleness of glass and ceramic coatings, cracks and delamination may easily develop in thin films when the substrate is subjected to plastic deformation. This may be localized, due to impact with hard objects, or may be extensive due, for example, to bending of the substrate. Cracks may also develop because of transformations in the substrate, like the previously discussed precipitation of carbide crystals during thermal treatment. For many applications, like thermal barriers, protection from abrasion, wear and highly corrosive media, very thick layers are usually required. However, inorganic sol-gel coatings thicker than 0.3-1 /zm, depending on the nature and composition of the film, crack during drying or thermal treatment as discussed before. Drying problems may be partially overcome by multilayer deposition or by using fillers to reduce

the shrinkage of the gel [32], but problems related to thermal expansion mismatches remain. These could be removed by choosing a material with a thermal expansion as close as possible to that of the substrate, or able to relax all stresses at the temperature of thermal treatment (i.e., a glass above Tg). These aspects were taken into consideration in the development of an interesting patent [46], where a method for repairing glasslined equipments based on the sol-gel process is described. Thicker coatings can be produced with organically modified ceramics (ormocers), but the applicability of these materials is limited by their thermal weakness and by the mechanical properties which, although superior to those of polymers, are not as good as those of ceramics. Izumi et al. [2, 36] coated stainless steel with methyltrialkoxysilane-derived films and observed that forming (bending, impact, drawing, pressforming) was possible, without peeling, when the films were treated between 200 and 300~ Heat treatment at higher temperatures greatly improved microhardness and abrasion resistance, but was deleterious for adhesion and decreased the flexibility. Most studies reported in the literature were performed on planar samples, depositing the films by dip or spin coating. Objects with complex shapes are more difficult to coat by these methods, especially if thickness uniformity is a strict requirement. For this reason other coating methods should be more extensively investigated. An interesting alternative is electrophoresis. Few reports have been published on the use of electrophoresis for sol-gel coating. Zhang et al. [39] compared thin aluminoborosilicate coatings deposited on A1 by electrophoresis and by dip-coating. They found that electrophoretically-deposited films had larger refractive indexes, probably due to higher densities. Indeed, electrophoresis is likely to produce denser layers because the particles move preferentially towards pinholes in the film, where the electric field is higher, and impact on the surface with a finite velocity. Electrophoresis may also be useful for the deposition of thick layers. Guglielmi et al. [32] coated stainless steel with zirconia coatings exceeding 10/zm thickness, by using a suspension of submicronic zirconia powder in a zirconium alkoxide solution. Electrophoresis experiments have been reported for depositing also thick organically modified layers [9]. Spraying techniques are also interesting when good optical qualities of the coating are not a critical

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3. M. Mayrand, J.F. Quinson, M. Pauthe, M. Lacroix-Repellin, E Gaillard, and G. de Marignan, 1st European Work~hop on Hybrid Organic-Inorganic Materials (Chateau de Bierville, 1993), p. 313. 4. C,S. Ashley, S.T. Reed, and A.R. Mahoney, Mat. Res. Soc. Symp. Proc. 121,635 (1988). 5. O. De Sanctis, L. Gomez, N. Pellegri, C. Parodi, A. Marajovsky, and A. Duran, J. Non-Cryst. Solids 121,338 (1990). 6. P. Innocenzi, M. Guglielmi, M. Gobbin, and P. Colombo, J. Europ. Ceram. Soc. 10, 431 (1992). 7. K. Izumi, H. Tanaka, Y. Uchida, N. Tohge, and T. Minami, J. Non-Cryst. Solids 147&148, 483 (1992). 8. C.J. Brinker, W.L. Warren, M.N. Logan, and C.S. Ashley, Mat. Res. Soc. Symp. Proc. 284, 469 (1993). 9. H. Schmidt and H. Wolter, J. Non-Cryst. Solids 121, 428 (1990). 10. D.A. Jones, Principles and Prevention of Corrosion (Macmillan Publishing Company, Singapore, 1992). 11. B.A. Pint, MRS Bull. XIX, 26 (1994). 12. K. Izami, M. Murakami, T. Deguchi, A. Morita, N. Tohge, and T, Minami, J. Am. Ceram. Soc. 72, 1465 (1989). 13. R. Di Maggio, P. Scardi, and A. Tomasi, Mat. Res. Soc. Symp. Proc. 180, 481 (1990). 14. M. Atik and M.A. Aegerter, Mat. Res. Soc. Symp. Proc. 271, 471 (1992). 15. K. Miyazawa, K. Suzuki, and M.Y. Wey, J. Am. Ceram. Soc. 78, 347 (1995). 16. M. Guglielmi, D. Festa, P. Innocenzi, P. Colombo, and M. Gobbin, J. Non-Cryst. Solids 147&148, 474 (1992). 17. M. Guglielmi, D. Festa, P. Innocenzi, L. Mancinelli Degli Esposti, N. Maliavski, and E. Tchekounova, Cer. Acta 7, 31 (1995). 18. N. Maliavski, E. Tchekounova, P. lnnocenzi, D. Festa, M. Guglielmi, L. Mancinelli, and Degli Esposti, J. Europ. Ceram. Soc. 15, 337 (1995). 19. A.G. Williams and L.V. Interrante, Mat. Res. Soc. Syrup. Proc. 32, 151 (1984). 20. S.T. Reed and C.S. Ashley, Mat. Res. Soc. Symp. Proc. 121, 631 (1988). 21. A. Morales and A. Duran, presented at the 7th Int. Symp. on Solar Thermal Concentrating Technologies, Moscow, 1994. 22. A. Morales and A. Duran, this Workshop. 23. O. De Sanctis, L. Gomez, N. PeUegri, and A. Duran, Surf. Coat. Technol. 70, 251 (1995). 24. M. Shane and M.L. Mecarteney, J. Mater. Science 25, 1537 (1990). 25. P. De Lima Neto, M. Atik, L.A. Avaca, and M.A. Aegerter, J. Sol-Gel Sci. Technol. 2, 529 (1994). 26. P. De Lima Neto, M. Atik, L.A. Avaca and M.A. Aegerter, J. Sol-Gel Sci. Technol. 1, 177 (1994). 27. J. de Damborenea, A. V~quez, N. Pellegri, O. de Sanctis, and A. Dur~.n, J. Sol-Gel Sci. Teehnol. 4, 247 (1995). 28. C. Chino, M. Charbonnier, A.M. de Becdelievre, C. Guizard, M. Panthe, and J.F. Quinson, Eurogel'91, edited by S. Vilminot, R. Nass, and H. Schmidt (Elsevier Science Publishers, B.V., Amsterdam, 1992), p. 327. 29. K. Kato, J. Mater. Science 27, 1445 (1992). 30. K. Kato, J. Mater. Science 28, 4033 (1993). 31. R. Kasemann and H. Schmidt, 1st European Workshop on Hybrid Organic-Inorganic Materiab (Chateau de Bierville, 1993), p. 171

requirement. Di Giampaolo Conde et al. [37] deposited thick aluminosilicate coatings on steel by wet-spraying and thermal spraying. The last method was completely different from traditional methods used in sol-gel technology: they used gel-derived powders, instead of liquid solutions, which were injected into the hot gas stream of an oxy-acetylene torch. Microstructural modification of metal substrates may occur during thermal treatment. An example is given by stainless steel heated between 450 and 850~ chromium carbides precipitate at the grain boundaries, with depletion of chromium and sensitization to intergranular corrosion. This problem could arise during thermal densification of sol-gel coatings. De Sanctis et al. [23] found that no sensitization was produced on heating coated stainless steel 1 h at 500~ However, higher temperatures or longer times may sensitize the steel, canceling any beneficial effect of the coating.
4. Conclusion

Sol-gel coatings on metals are an interesting field of research. However, attention must by paid to problems intrinsic to sol-gel processing or specific of coating/metal systems, which limit, in some cases, the practical applications. Sol-gel coatings may protect metals from oxidation. In this contest, the possibility to deposit homogeneous films containing reactive elements should be considered as an interesting alternative to barrier layers. Much more difficult is the task of increasing wet corrosion resistance. In this case, thicker and crackfree coatings should be produced. Organically modified films may be a solution for low temperature applications. Often, traditional sol-gel coating methods (dip and spin coating) are not suitable for coating complex metallic objects. Alternative techniques should be experimented or developed, in order to give better chances for application.
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