Int. J. Appl. Ceram. Technol., 17 (2014) DOI:10.1111/ijac.

12230

Solgel-Processed Mullite CoatingA Review

Jagannath Roy*
Camellia Institute of Technology, Kolkata 700129, India

Santanu Das and Saikat Maitra

Government College of Engineering & Ceramic Technology, Kolkata 700010, India

Mullite is one of the popular ceramic materials for different engineering applications due to some of its important properties which include good thermal and chemical stability, high creep resistance, etc. Mullite synthesized by solgel process generally requires lower temperature for processing and generate product with better homogeneity and more purity compared with other conventional processes. Coating of solgel-derived mullite lm on surface of a ceramic substrate can improve its thermomechanical properties, making it suitable for applications in different aggravated conditions. This study embarks a comprehensive review on synthesis, characterization and applications of solgel-derived mullite coating.

Introduction A sol is a colloidal suspension of solid particles in a liquid. Sols can be converted to gel by maintaining proper reaction condition. The wet gel after drying and proper grinding can be transformed into powder form. This type of powder preparation technique is termed as solgel method. Detail knowledge on the solgel process can be acquired from the book authored by Brinker and Scherer.1 Coating is a process to make a layer having thickness generally from submicrometer to nanometer range of a substance spread over a surface. Coatings are used to modify the morphology of a surface to improve properties such as thermal, mechanical and chemical stability, durability or lifetime. Although there are a number of techniques such as vapor deposition, plasma-assisted/ionbeam-assisted deposition, and atomic layer deposition to coat planar surfaces, solgel process has the unique feature for complex shape coating in nanometer to micrometer scale.2,3 Ceramic materials are used in coating process due to high hardness and inertness of such materials. Mullite is one of the popular ceramic materials and it is the only thermodynamically stable phase in the Al2O3-SiO2 binary system with composition varies from 3:2 to 2:1.4,5 It is basically a nonstoichiometric compound with molecular formula Al2[Al2+2xSi22x]O10x , where x denotes the number of missing oxygen atoms per unit cell.6,7 Mullite was rst discovered on the Isle of Mull, situated at the west coast of Scotland. Although occurs very rarely in
*royj007@rediffmail.com 2014 The American Ceramic Society

nature, mullite presents extensively as the major crystalline phase in heat-treated ceramic products developed from naturally occurring aluminosilicate minerals such as china clay and sillimanite. In laboratory, mullite can be synthesized by several techniques. Mullite synthesized by solgel process is known as chemical mullite.8 Employing solgel process, product with better homogeneity and purity can be expected at relatively lower temperature (between ~980 and 1350C) compared with that (temperature 1450 1800C) required for traditional processes.911 Mullite has several remarkable properties which include excellent heat resistance, high strength and toughness, good thermal and chemical stability, low thermal expansion coefcient, high creep resistance, etc.1217 Owing to these important qualities, mullite are widely used in the production of refractory material, optical and electrical components, electronic packaging, biological processes, 1822 etc. One of the most recent applications of mullite is in coating technology. Coating of solgel-processed mullite lm on surface of a substance can make it suitable for applications in different reaction conditions. In the rst segment of this study, a review has been carried out on some of the many studies about synthesis and characterization of solgel-processed mullite precursor coating on different surfaces. Then, various applications of mullite coating and future prospects of such coating with solgel-derived mullite have been discussed.

Synthesis of Mullite Precursor In solgel methods, mullite precursor is formed either from admixture of alumina and silica sols or admixture

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of these sols and salts. The latter process is advantageous because precipitation of hydroxide from the salt components on the surface of the sol particles act as heterogeneous nucleation sites. These sites help in effective mullitization process.8 Again, level of homogeneity plays an important role as it controls the distance of chemical interdiffusion path lengths and consequently formation of mullite crystalline phases.23 So choice of precursor plays an important role in this process. A variety of precursors have been used by different researchers for the synthesis of mullite and some of these are summarized in Table I. Gelation largely depends on factors such as (i) degree of homogeneity (ii) extent of hydrolysis and condensation, and (iii) pH of the medium. ANN and TEOS have been found to be the most popular precursors after Rustum Roy used these two for mullite synthesis rst time in 1958.2430 Some researchers used sodium silicate or metasilicate to generate silicic acid through ion exchange process.3234,37,38,42 Other sources of starting materials include inorganic salts of alumi-

Table I. Examples of Precursors used in Solgel Process for Mullite Precursor Synthesis Reagents ANN + TEOS + Water + EtOH ANN + TEOS + Water ANN +TEOS+ EtOH ANN + TEOS +AIP+ Water ANN + AIP+ Water+ EtOH ANN + Sodium metasilicate + Urea ANN + Silicic acid + Urea ANN + Silica sol+ +Water ANN + Colloidal silica + Water + NH3 ANN + Sodium metasilicate + Water + Ethylene glycol ANN + Sodium silicate + Water + NH3 Boehmite + TEOS + Water AIP + TEOS + Water +EtOH Aluminum nitrate + TEOS + Water +EtOH Solid aluminum nitrate + Sodium metasilicate + Water + Urea Sodium aluminate + Sodium silicate pentahydrate + Water AlCl36H2O+TEOS + Water + Alcohol AlCl36H2O + TEOS + EtOH + Water References 25, 26 27,28 29 30 31 32, 33 34 35 36 37 38 39 40 41 42 43 44 45

AIP, aluminum isopropoxide; ANN, aluminum nitrate nonahydrate; EtOH, ethanol; NH3, ammonia; TEOS, tetraethyl orthosilicate.

num and silicon or organic species as their alkoxide. In some of these processes, a single solution was prepared by dissolving stoichiometric amount of aluminum- and silicon-bearing precursor in a solvent and then it was reuxed. In other cases, separate solutions were prepared by dissolving stoichiometric amount of aluminum- and silicon-bearing precursor in a particular solvent and then two solutions were mixed. Ammonia solution was added with constant stirring to complete the precipitation of gel. Selection of a particular solvent is also important as it controls the effective interaction between alumina and silica particles during heat treatment, leading to mullite formation. Mostly, water and ethanol were used as the solvent, but in few cases, methanol, isopropanol, diethyl ether, etc. were also used as solvent.46,47 Depending on the homogeneity, mullite precursor gel can be classied into two categories, namely monophasic and diphasic gel. Monophasic gel is formed during true precipitation, that is, continuous condensation growth of species with aluminosiloxane (-Al-O-Si-) bond.4854 In such system, homogeneity is achieved at the atomic level and orthorhombic mullite is obtained at around 980C. Nucleation is the rate controlling step toward mullitization, and the activation energy of crystallization process for mullite varies from 300 to 400 kJ/ mol. But mullite formation can also possible at high temperature (~1000C) with high activation energy (1400 kJ/mol) from monophasic gel.55 Formation of diphasic gel is the example of coprecipitation process where silicon and aluminum hydroxide are precipitated side by side.44,5661 Homogeneity is maintained in the nanometer range, and mullitization process followed nucleation and growth mechanism.22 Relatively higher sintering temperature (~1300C) and higher activation energy (~1000 kJ/mol) are required for mullite crystallization. One advantage of diphasic gel system over monophasic is that in case of the former, the heat of reaction of the different phases provides extra energy for the densication process.62 Another type of gel formation is also possible which can be resulted by the combination of monophasic and diphasic system and this type of gel is termed as hybrid gel.63,64 During solgel process, both aluminum- and siliconcontaining compounds undergo hydrolysis and/or condensation reaction. The hydrolysis and condensation reactions depend on several reaction conditions such as reactant concentrations, solution pH, and temperature.8,65 Complete hydrolysis of silicon and aluminum alkoxides takes place by the following ways:

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Solgel-Processed Mullite Coating

Si(OR)4 4H2 O ! Si(OH)4 4ROH Al(OR)3 3H2 O ! Al(OH)3 3ROH

1:1 1:2

Aluminosiloxane (-Si-O-Al-) bonds are formed due to the following condensation reaction Si(OH)4 Al(OH)3 ! OH3 Si O Al(OH)2 H2 O 2 Condensation reaction may also leads to the formation of Si-O-Si- and Al-O-Al- bonds. But there rates of formation have to be minimized to avoid subsequent segregation. Si(OH)4 Si(OH)4 ! OH3 Si O Si(OH)3 H2 O 3:1 Al(OH)3 Al(OH)3 ! OH2 Al O Al(OH)2 H2 O 3:2 To avoid segregation, following points need to be considered to control the rate of hydrolysis: 1. A prehydrolysis step should be carried out with silicon-containing compounds as these compounds have lower rate of hydrolysis compared with corresponding aluminum-containing compounds. 2. Water addition should carried out carefully. 3. Base addition should be controlled at the early stage of hydrolysis as such addition can lead to faster segregation.8,65 The stability of sols depends largely on the pH of the medium. Except for strongly acidic and basic medium, alumina sol is stable over a wide pH range. But the stability of silica sol is varied regularly with the change of pH. Silica sol is maximum stable at pH ~ 2. Thereafter, it stability decreases up to pH ~ 6. Then, its stability again increases up to pH-10. So for mixing of silica and alumina sol, the adequate ranges of pH are 2 and 910.8 For monophasic gel formation, pH of the mixed sol should be between 3 and 4.5, whereas for diphasic gel, it should be 1 and 14.66,67

Fabrication and Characterization of Mullite Coating The most common method used for coating by mullite precursor sol is dip coating. But other techniques such as spin coating, plasma spray coating, and vacuum ltration are also used. The detail knowledge on different coating techniques can be obtained from the literature.6870

Solvent evaporation is one of the important steps in solution-based coating. The solvent evaporation is greatly control by the atmospheric conditions such as temperature and humidity. The sol particles are stabilized by surface charges, and after the evaporation of the solvent, sols are converted to gel. During gelation, coherent force acting within the lm cause shrinking of the bonds between sol particles and substrate surface. It generates tensile stress which can damage the lm formed. Magnitude of the tensile stress depends upon the thickness of the lm. During densication, in the case of highly thicker lm, the coherent force will cause the lm to shrink in the direction parallel to the substrate surface and can develop crack in the lm. But for thinner lms, shrinking perpendicular to the surface results strong attachment of the lm to the surface.71 The coating thickness largely depends upon the viscosity of the solution. Viscosity of the solution increases with time and tendency of the solution to stick to the substrate surface increases as the viscosity of the solution increases. As a result, there will be a higher concentration of silicon-containing molecules, resulting in the formation of glassy phase during densication. Therefore, it is best to use a newly prepared solution. The solvent/precursor ratio also affects the density of the nal lm. Solution with higher water content generally exhibit higher hydrolysis reaction rates producing a more highly condensed polymer. Therefore, a reduction in the solvent/precursor ratio makes the lm thicker.71 Once coated, the lm must be densied at a higher temperature to develop a compact and smoother surface. During the shrinking of the gel, its network is continuously deformed and the remaining liquids are transported out from the lm through pores. This develops stress and strain in the shrinking gel. Higher temperature requires for mullitization will collapse the pores and reduce the surface energy, making the lms dense and smooth. Densication also has the added benet of driving out organic residue.71 Different instrumental techniques were applied to study the mullitization process after coating. Chen and Wei72 synthesized mullite (3:2) precursor sol using tetraethyl orthosilicate (TEOS) and boehmite to coat crackfree lms having grain sizes ranges from 0.1 lm to a few micrometers on silica substrates by spin coating at a speed of 5000 rpm for 10 second. Polyvinylpyrrolidone (PVP) was used as a crack-limiting agent. Initial viscosity was ~10 cps and it reached to ~50 cps at the gelation point. The lm was dried at 25C for 24 hours and heat-treated up to 1300C. Mullite formation started at 1280C, and at this stage, wavy nature of grain boundary of mullite grain conrmed diphasic nature of the

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mullite. Again, irregular distribution of mullite grains indicated that the overall mullitization is still incomplete. Stoichiometric mullite precursor was synthesized by solgel process using ANN and TEOS and coated on porous silicon carbide surface by dip-coating method.73 Orthorhombic mullite formation was almost completed at 1200C, and mullite lms with average pore diameter and porosity about 4.5 lm and 52.3%, respectively, were distributed on silicon carbide surface. Noritake et al.74 used dip-coating process to coat mullite lm on -SiAlON (Si6zAlzOzN8z, z = 3) ceramics. At rst, the Al2O3 lm was synthesized from alumina sol and then it was deposited on polished -SiAlON ceramics. The coated sample was heated in Ar/O2 (95/5 vol%) atmosphere at 1300C for 2 hours. During heat treatment, reaction between Al2O3 and silica from sialon produced mullite which formed a layer over the surface of the substrate. This coated layer enhanced the oxidation resistance of sialon. SiC coated with diphasic mullite was synthesized by solgel route using ANN and TEOS.75 SiC suspension was mixed into mullite precursor sol and to this solution dil. NH3 solution was added dropwise until the pH was raised to 7.5. After ltration and proper washing, coated powder was dried in an air oven at 80C. Dilatometric studies indicated that the maximum shrinkage of the coating solution occurred in the temperature range of 12701300C. The hardness of the composite having 5 vol% SiC was almost 1300 kg/mm2. When concentration of SiC is increased, grain growth was inhibited due to the dispersion of SiC at the grain boundaries. Microporous and dense mullite coating having thickness of 80100 nm was developed over SiC particles which protected SiC from oxidation at higher temperatures. Ansar et al.76 synthesized hybrid mullite precursor sol using hydrous aluminum nitrate and TEOS employing solgel route to coat over graphite surfaces. Mullitization process was studied by DTA and XRD analysis. Mullite formation was completed at around 1200C. Such mullite coating improves oxidation resistance and water wettability of graphite signicantly. Xu et al.77 added Yb2Si2O7 on mullite coated over silicon carbide ceramic matrix composites (SiC-CMCs) to protect such composites from oxidation. By applying atmospheric pressure plasma spraying (APPS) process, Si layer was developed on SiC-CMCs, and then, Si-SiCCMC was dipped into mullite precursor sol synthesized by employing solgel process using ethyl silicate and aluminum nitrate for 10 minutes. Now mullite layer formed by thermal treatment and then again by APPS, Yb2Si2O7 layer was coated on mullite layer. XRD and thermal analyses (DTA and TGA) were performed to

determine the coating components, phases, loss of gravity, and crystalline transformations. The thickness of the coating was in the micrometer range (2530 lm). Uniform, close-grained and crack-free layers with excellent adherence were developed. Oxidation resistance of SiC was also increased with the increase in dipping and spraying time. Jayasankar et al.78 synthesized diphasic mullite precursor sol by stirring a stoichiometric mixture of boehmite sol and TEOS having pH ~ 3.5. Boehmite sol was prepared by peptization of ANN solution with HNO3 at pH 3 to 3.5. The initial viscosity of sol having particle size of 170 nm was ~6 cps with shear rate of 800/seconds. Coating on SiC was performed by vacuum ltration. The complete crystalline of mullite occurred at 1300C, and spherically shaped mullite grains were uniformly coated over SiC substrate.

Application of Mullite in Coating Technology Mullite coating has the most emerging application in thermal barrier coating (TBC) and environmental barrier coating (EBC). As mullite (Al2O32SiO2) can retain its high-temperature strength, low thermal conductivity, favorable creep behavior, and chemical stability at very high temperatures, mullite composite coatings are being used in TBC for application in space vehicles. The wide range of materials used in these composite coatings includes mullite/alumina, mullite/zirconia, mullite/silicon carbide, mullite/molybdenum.7983 Advanced gas turbine running at higher temperatures is used for power generation to meet increased demand of electricity. To develop new generation turbines and micro turbines, major concerns are economical and environmental aspects, that is, improving efciency and reducing emissions. To achieve higher inlet temperatures, advanced technology is required for cooling, materials improvement, and coatings.84 In gas turbine material development, TBC plays a signicant role. TBC made by ceramic material with very low thermal conductivity reduces the alloy surface temperature by insulating it from the hot gas. TBC consist two layers of metallic bond coat and ceramic top coat.85 The bond coat protects the super alloy from environmental degradation by forming bonds between the ceramic top coat and the super alloy substrate. Ceramic top coat is used to protect metallic components from high temperatures, thereby increasing the lifetime of these components and allowing higher operating temperatures. Because of high melting point, high thermal expansion

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Solgel-Processed Mullite Coating

coefcient, low thermal conductivity, etc., yttria-stabilized zirconia (YSZ) composite is used as top coat. Again YSZ is thermodynamically stable in contact with alumina that grows on bond coat.86 Addition of YSZ to mullite can improve its thermal shock resistance and creep resistance, and mulliteYSZ composite can be used as improved TBC material by combining the advantageous properties of mullite with those of YSZ.8789 SiC ceramic matrix composites (SiC-CMCs), having low density, superior high-temperature strength and durability, become promising hot section materials in gas turbine aeroengine.9092 These materials present excellent high temperature oxidation resistance due to the growth of the protective silica layer under dry condition. But in gas turbine engines, excessive heat and steam results corrosion. This leads to surface recession through the destruction of the SiO2 layer and nally dimensional changes in this ceramic component.9395 To protect Si-based ceramics and ceramic composites, a new class of coatings, termed as EBC, comprises of silicon bond coat, a mullite-based intermediate coat, and a bariumstrontiumaluminosilicate (1xBaOxSrOAl2O32SiO2, 0 x 1) top coat has been developed. For a successful EBC, the main requirements are environmental stability particularly in water vapor, compatible value of coefcient of thermal expansion (CTE), phase stability, a low thermal conductivity for maximum thermal insulation capability, etc.91,96,97 Mullite (3Al2O32SiO2) coatings has attracted most interest as a protective coating for Si-based ceramics because its good CTE match, chemical compatibility with SiC and Si3N4 ceramics, and also it creates less defects.91,98100 Carbon/carbon(C/C) and carbon/carbonsilicon carbide (C/CSiC) composites are ideal high-temperature structural materials for various engineering and aerospace applications as these materials possess many interesting properties which include lightweight, good thermal shock resistance, and excellent mechanical properties. Again, these materials do not lose strength as the temperature increases. So these materials are extensively used as on the nose caps and leading edges of space vehicles, disk brakes, turbine engines, electrical contact, heating unit, fusion reactors, hypersonic vehicles, propulsion systems, etc. But due to oxidation of such materials after 450C, such applications become limited.101 Antioxidative protective coating made by mullite is the best way to enhance the service life of these materials.102105 Mullite can also be used to coat the graphite surface efciently to improve graphites oxidation resistance, and this coated graphite may be incorporated in refractory composites for both ferrous and nonferrous metallurgical conditions.106

Advantages of Solgel Techniques for Mullite Coating Solgel process has the superiority over traditional processes in terms of intimate mixing of the components and consequently the development of homogeneity of the nal product. Mullite synthesized by solgel process can be obtained at a lower temperature compared with processes like CVD or solid-state sintering. During coating by solgel-processed mullite, coated specimen adhere well with substrate surface resulting uniform, crack-free surface.7278 Conventional plasma spraying for mullite coating leads to the development of a relatively large amount of amorphous phase in the coating. Crystallization of these phases at elevated temperatures results excessive cracking and debonding.98 Crack generation is also possible in solgel process during shrinkage between the coating layer and surface of the substrate, but this disadvantage can be eliminated using additives like a chelating agent or diols. Suitable additives retard the condensation reaction and promote structural relaxation in the coated lm.108,109 Again in solgel process, homogenous lm formation can be performed at low cost price compare with other processes.2,107

Conclusion Coating is a process to make a thin layer on a surface of a substance to enhance its lifetime by improving its thermal and mechanical properties, chemical stability, durability, etc. Ceramic materials particularly mullite has the potentiality to act as good coating substance because of its high hardness and inertness. Mullite precursor synthesized by solgel process can produce crack-free homogeneous lms at relatively low cost and such coating can be extensively used in TBC and EBC to protect silicon and carbon-based composite materials.

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