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Aluminum oxide also forms ternary and mixed-metal oxide phases. Ternary systems such as mullite (Al 6 Si 2 O 13 ), yttrium aluminum garnet (YAG, Y 3 Al 5 O 12 ), the β - aluminas (e.g., NaAl 11 O 17 ) and aluminates such as hibonite (CaAl 12 O 19 ) possessing β -alumina or magnetoplumbite-type structures can offer advantages over those of the binary aluminum oxides.

Applications of these materials are found in areas such as engineering composite materials, coatings, technical and electronic ceramics, and catalysts. For example, mullite has exceptional high temperature shock resistance and is widely used as an infrared-transparent window for high temperature applications, as a substrate in multilayer electronic device packaging, and in high temperature structural applications. Hibonite and other hexaluminates with similar structures are being evaluated as interfacial coatings for ceramic matrix composites due to their high thermal stability and unique crystallographic structures. Furthermore, aluminum oxides doped with an alkali, alkaline earth, rare earth, or transition metal are of interest for their enhanced chemical and physical properties in applications utilizing their unique optoelectronic properties.

Synthesis of aluminum oxide ceramics

In common with the majority of oxide ceramics, two primary synthetic processes are employed for the production of aluminum oxide and mixed metal oxide materials:

  1. The traditional ceramic powder process.
  2. The solution-gelation, or "sol-gel" process.

The environmental impact of alumina and alumina-based ceramics is in general negligible; however, the same cannot be said for these methods of preparation. As practiced commercially, both of the above processes can have a significant detrimental environmental impact.

Traditional ceramic processing

Traditional ceramic processing involves three basic steps generally referred to as powder-processing, shape-forming, and densification, often with a final mechanical finishing step. Although several steps may be energy intensive, the most direct environmental impact arises from the shape-forming process where various binders, solvents, and other potentially toxic agents are added to form and stabilize a solid ("green") body ( [link] ).

Typical composition of alumina green body
Function Composition Volume (%)
Powder alumina (Al 2 O 3 ) 27
Solvent 1,1,1-trichloroethane/ethanol 58
Deflocculant menhaden oil 1.8
Binder poly(vinyl butyrol) 4.4
Plasticizer poly(ethylene glycol)/octyl phthalate 8.8

The component chemicals are mixed to a slurry, cast, then dried and fired. In addition to any innate health risk associated with the chemical processing these agents are subsequently removed in gaseous form by direct evaporation or pyrolysis. The replacement of chlorinated solvents such as 1,1,1-trichloroethylene (TCE) must be regarded as a high priority for limiting environmental pollution. The United States Environmental Protection Agency (EPA) included TCE on its 1991 list of 17 high-priority toxic chemicals targeted for source reduction. The plasticizers, binders, and alcohols used in the process present a number of potential environmental impacts associated with the release of combustion products during firing of the ceramics, and the need to recycle or discharge alcohols which, in the case of discharge to waterways, may exert high biological oxygen demands in the receiving communities. It would be desirable, therefore, to be able to use aqueous processing; however, this has previously been unsuccessful due to problems associated with batching, milling, and forming. Nevertheless, with a suitable choice of binders, etc., aqueous processing is possible. Unfortunately, in many cast-parts formed by green body processing the liquid solvent alone consists of over 50 % of the initial volume, and while this is not directly of an environmental concern, the resultant shrinkage makes near net shape processing difficult.

Sol-gel

Whereas the traditional sintering process is used primarily for the manufacture of dense parts, the solution-gelation (sol-gel) process has been applied industrially primarily for the production of porous materials and coatings.

Sol-gel involves a four stage process: dispersion, gelation, drying, and firing. A stable liquid dispersion or sol of the colloidal ceramic precursor is initially formed in a solvent with appropriate additives. By changing the concentration (aging) or pH, the dispersion is "polymerized" to form a solid dispersion or gel . The excess liquid is removed from this gel by drying and the final ceramic is formed by firing the gel at higher temperatures.

The common sol-gel route to aluminum oxides employs aluminum hydroxide or hydroxide-based material as the solid colloid, the second phase being water and/or an organic solvent, however, the strong interactions of the freshly precipitated alumina gels with ions from the precursor solutions makes it difficult to prepare these gels in pure form. To avoid this complication, alumina gels are also prepared from the hydrolysis of aluminum alkoxides, Al(OR) 3 .

The exact composition of the gel in commercial systems is ordinarily proprietary, however, a typical composition will include an aluminum compound, a mineral acid, and a complexing agent to inhibit premature precipitation of the gel, e.g., [link] .

Typical composition of an alumina sol-gel for slipcast ceramics.
Function Composition
Boehmite precursor ASB [aluminum sec -butoxide, Al(OC 4 H 9 ) 3 ]
Electrolyte HNO 3 0.07 mole/mole ASB
Complexing agent glycerol ca . 10 wt.%

The principal environmental consequences arising from the sol-gel process are those associated with the use of strong acids, plasticizers, binders, solvents, and sec -butanol formed during the reaction. Depending on the firing conditions, variable amounts of organic materials such as binders and plasticizers may be released as combustion products. NO x ’s may also be produced in the off-gas from residual nitric acid or nitrate salts. Moreover, acids and solvents must be recycled or disposed of. Energy consumption in the process entails “upstream” environmental emissions associated with the production of that energy.

Bibliography

  • Advances in Ceramics , Eds. J. A. Mangels and G. L. Messing, American Ceramic Society, Westville, OH, 1984, Vol. 9.
  • Adkins, J. Am. Chem. Soc. , 1922, 44 , 2175.
  • A. R. Barron, Comm. Inorg. Chem ., 1993, 14 , 123.
  • M. K. Cinibulk, Ceram. Eng. Sci., Proc ., 1994, 15 , 721.
  • F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry , 5th Ed., John Wiley and Sons, New York (1988).
  • N. N. Greenwood and A. Earnshaw, Chemistry of the Elements , Pergamon Press, Oxford (1984).
  • P. H. Hsu and T. F. Bates, Mineral Mag ., 1964, 33 , 749.
  • W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics , 2nd Ed. Wiley, New York (1976).
  • H. Schneider, K. Okada, and J. Pask, Mullite and Mullite Ceramics , Wiley (1994).
  • R. V. Thomas, Systems Analysis and Water Quality Management , McGraw-Hill, New York (1972).
  • J. C. Williams, in Treatise on Materials Science and Technology , Ed. F. F. Y. Wang, Academic Press, New York (1976).

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Source:  OpenStax, Chemistry of electronic materials. OpenStax CNX. Aug 09, 2011 Download for free at http://cnx.org/content/col10719/1.9
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