Synthesis, Properties and Applications of Cordierite Ceramics, Part 1. Interceram
Synthesis, Properties and Applications of Cordierite Ceramics, Part 1. Interceram
Synthesis, Properties and Applications of Cordierite Ceramics, Part 1. Interceram
Anirban Chowdhury is a post-graduate research student working in the area of sol gel ferroelectrics for his PhD at the Institute for Materials Research, University of Leeds, UK. He earned his BTech in Ceramics from the College of Ceramic Technology, University of Calcutta and MTech in Materials Science from IIT Kanpur. He received the prestigious ORS award and a Tetley & Lupton Scholarship for 20052008.
Abstract
As an engineering material, cordierite has many applications in different fields exploiting its unique electrical, mechanical and thermal properties. The synthetic aspect of cordierite is of constant interest to researchers. Elucidation of its structure and establishing the properties of its structure has always been considered a fascinating subject by researchers. In the present paper these different aspects of cordierite are briefly reviewed. Keywords: Cordierite, processing, properties, applications
1 Introduction
Cordierite (2MgO2Al2O35SiO2) is an important naturally occurring ceramic material, which is popular especially for its unusually low thermal expansion coefficient, low thermal mass, low dielectric loss factor, low density, volume resistivity and high thermal shock resistance. Cordierite is isostructural with beryllium. It is found in two structural forms, namely, the orthorhombic (low temperature form) symmetry, which is more common, and the hexagonal symmetry, which is also known as indialite. The structure of cordierite is characterized by six-membered rings and is built up from SiO4 and AlO4 tetrahedra. These tetrahedra form six (cation) membered or four (cation) membered rings [1], as shown in Fig. 1.
Some properties of this multiphase oxide are given below [24]: Density 2.02.53 g/cm3 Melting point 1470 C Thermal expansion coefficient from 25 to 1000 C 1.42.6 106/K Youngs modulus 139150 GPa Flexural strength at room temperature 120245 Relative dielectric constant 5.0 (K and tan at 1 MHz) Typical thermal expansion curves are shown in Fig. 2. The expansion is small and anisotropic. The c axis expansion is negative, while the a axis expansion is positive and therefore the re-
sultant volume expansion is negligibly small (with an aggregate thermal expansion of about 0.9 106/K from room temperature to 800 C). With elevated temperatures, the increased thermal motion of the atoms of cordierite is accommodated primarily by twisting and rotation of the rings. The relationship between thermal expansion and crystal structure of cordierite has been discussed by Hochella and Brown [5]. Cordierite is widely used in the whiteware industries as kiln furniture because of its abovementioned properties. It also has advanced applications as electrical insulators, high performance resistors, heating element supports, burner tubes,feed-through insulators,special furnace shapes, exhaust catalyst supports, filters and many more that are discussed here. For engineering applications, it is usual to control purity and reproducibility by utilizing synthetic cordierite.
2 Mineralogical aspects
Cordierite is a magnesium aluminium silicate (Mg2Al4Si5O18) mineral. It belongs to the class of silicates and the subclass of cyclosilicates (andalusite-sillimanite-kyanite group).Although, it is not a very popular mineral from the geological point of view, its gemstone variety, which is called iolite, is well known among gemstone collectors and fanciers. Cordierite was known and used as a gemstone in Sri Lanka long before the French geologistmineralogist Pierre Louis Cordier accurately described it in 1809. Cordierite was identified as a specific mineral and named in 1813. Apart from iolite, the other varieties of cordierite found are bloodshot iolite and praseolite. The unusual blue-violet colour of cordierite is attractive Fig. 2 Typical thermal expansion curves of cordierite [5] and can be compared
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with a light blue sapphire of purplish tint. This is the reason why cordierite is sometimes called "water sapphire". Different colours of cordierite crystal available are blue, greyish blue, violet blue, grey, yellow, brown, green (rare), etc. One of the most notable characteristics of cordierite is its strong pleochroism, or colour changing ability. Generally, it is strongly trichroic. When viewed from one direction, the crystal or gemstone may appear blue or blue-violet. But as the crystal or gemstone is rotated in another viewing direction, the colour will appear yellowish gray to light blue. The Mg-rich variety shows as pale yellow, pale blue, and violet blue and the Fe-rich variety shows as colourless and violet. Its index of refraction varies in between 1.521.57. Its birefringence ranges from 0.005 to 0.018 and dispersion is 0.017. Its optical character is biaxial positive, but often it is negative. The crystals may be colourless or transparent to translucent. It has some opalescence resembling star sapphire. It has a vitreous lustre. The cleavage is poor in one direction and the fracture is subconchoidal. Its hardness is 77.5, specific gravity is approximately 2.3 and streak is white. It reacts slightly with concentrated acids, but more readily dissolves in HF. The crystal habits include rare prismatic crystals that are usually massive, or in compact grains embedded in metamorphic schists and gneisses. They are also found as pebbles and grains in alluvial deposits.The minerals associated with cordierite are almandine, corundum, andalusite, biotite and feldspars. The inclusions in cordierite crystals are clouds of very small zircon crystals surrounded by interference colours rimmed with intense yellow and hematite platelets in parallel orientation. Its notable occurrences include Sri Lanka; India; Burma; Madagascar; Middlesex Co., Connecticut and the Yellowknife area of the Northwest Territories of Canada.It is a very common mineral in Sweden as it is a component in many Swedish schists, found in central Sweden. It is of relatively low cost, has good electrical insulation properties, moderate mechanical properties and temperature resistance, and can readily be formed into a variety of shapes. It can be made in high volume through cost-effective extrusion or dry-pressing methods. through various routes. The effects of different additives like TiO2, ZrO2, ZnO, SrO, B2O3, etc. on the densification of cordierite have also been studied extensively. During powder preparation of cordierite the kinetics of heat treatment can also have a significant effect on its densification. Cordierite can be synthesized by firing traditional ceramic raw materials like clay, talc, silica and alumina at 13401450 C.But this process does not yield theoretically dense bodies as they cannot be fired to maturity due to excessive formation of glass from talc and clay and because of the fact that cordierite incongruously melts at 1460 C to give mullite. To overcome this problem, a cordierite composition is pre-calcined to grog (talc + alumina) and then combined with clay. Sometimes, the batch composition is melted and after fabrication of the desired shape directly from the melt or glass, the amorphous shape is devitrified to yield a cordierite monolith [6]. The conventional formation of cordierite involves two stages. Firstly, a small amount of cordierite is formed at 1275 C through the solid-state reaction of mullite, protoenstatite and cristoballite the decomposition products of talc and kaolinite. In the second stage, a glassy phase appears at 1335 C from the reaction of previously formed cordierite and the remaining cristoballite and protoenstatite. The bulk of the cordierite is then formed by the reaction of the melt with mullite. Cordierite forms at lower temperatures (1140 C) when clinochlore and kaolinite are reacted [7]. Al(NO3)39H2O and colloidal silica by co-precipitation method and studied its sintering. In other works, Han and Park [1112] synthesized and sintered cordierite from metal alkoxides,using Si(OC2H5)4Al(OC3H7)3Mg(OC2H5)2 by the sol-gel method. Densification of this powder compact, which was studied by using the precursor powders calcined at 900 C for 2 h, improved at the sintering temperature of 800900 C. An alkoxide sol-gel route was developed by Tsai [13] to prepare stoichiometric cordierite fibers. X-ray diffraction analysis revealed that non-aged and aged fibrous gels all remained amorphous at 800 C, but began crystallizing into -cordierite and -cordierite at 900 C and 1050 C, respectively. Single-phase -cordierite fibers were obtained at 1300 C. Heating the non-aged fibers yielded denser microstructures with fine grain sizes of 0.2 and 0.4 m,whereas the aged fibers exhibited porous microstructures following heating at 1300 C.A higher heating rate and aging treatment resulted in higher open porosity of the fired fiber. Petrovic et al [14] synthesized alkoxy-derived cordierite gels from tetraethylorthosilicate (TEOS), aluminium isopropoxide and magnesium ethoxide. TEOS was partially hydrolyzed at molar ratios H2O/TEOS = 1.2 in the presence of HCl as catalyst.At first -cordierite crystallized in a three dimensional growth at 9501000 C with a small amount of spinel. The transformation of - to -cordierite began at about 1100 C and that of - to cordierite occurred at above 1300 C. The overall activation energy of the crystallization of cordierite is 580 81 kJ/mol. Fukui et al [15] studied the effect of prehydrolysis on the structure of a complex alkoxide as a cordierite precursor and its crystallization behavior. Here complex alkoxides were synthesized as cordierite precursors by reaction of pre-hydrolysed TEOS with Al and Mg alkoxides and the effect of prehydrolysis on alkoxide structure was analyzed by IR, 27Al and 29Si NMR spectroscopies. It was observed that, for temperatures at the lower end of the range of -cordierite formation, an increase in the water ratio of prehydrolysis was effective because Si-O-Al bondings were introduced into the Mg-Al-Si complex alkoxides. Moon and Kim [16] prepared a cordierite ceramic with a thermally stable pore structure by a simple modification of a sol-gel reaction of alkoxide precursors, synthesized from Mg metal or Mg-acetate, Al(i-Opr)3 and partially pre-
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hydrolyzed Si(OEt)4. The crystallization of -cordierite began at 900 C and -cordierite formed in between 10501250 C. Lee and Kriven [17] synthesized homogenous and stable amorphous type cordierite powder by a solution-polymerization route using polyvinyl alcohol (PVA) solution as polymeric carrier. The bulky, long chain polymeric precursor changed into a very soft and porous powder after calcination at 800 C for 1 h. The calcined powder was attrition milled to get a 30 nm size amorphous cordierite powder with a high specific surface area (181 m2/gm).A dense powder having a relative density of 99 % and a CTE value of 2.1 106/C was found in the process. Awano et al [18] studied the effects of grinding on the synthesis of cordierite where a precursor gel derived from colloidal processing was ground. The calcined ground powder enhances the homogeneity of the resulting powder and causes the accumulation of internal energy as crystal strength; consequently the densities of the sintered bodies increase and the optimum temperature range widens. by the presence of crystalline particles in the fly ash, which jeopardized the viscous flow densification mechanism. These materials have good machinability.
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terials, mixing them in definite proportions, using additives in definite amount, etc. Different processes of synthesis will lead to the acquisition of definite properties in the cordierite ceramics. Some of these have been discussed in the previous section and will be discussed further in this section. shown to be chiral in nature and the chirality direction is fixed. The sandwich fillingappears in two shapes a thick,well-defined domain at low temperatures and a thin layer of wetting at high temperatures. Matos et al [31] studied the structure of polymeric and polymer-derived ceramic cellular cordierite foams using two different approaches, which were compared. The authors measured the morphological aspects of both structure from images acquired by optical and electron microscopy. In what concerns the cell structure, a relation was observed either in the proportion of the closed faces or in the size distributions of the cells. Average cell diameters ranged from 575 to 715 m in the ceramic foams and 715 to 920 m in case of polymeric foams. The size distributions of the ceramic cells were narrower than those of the respective polymer templates. The authors established a relation between the final ceramic structures and the respective templates and also explained the mechanical behaviour of the foams obtained. Diaz-Mora et al [32] investigated the activation energy and activation enthalpy for crystal growth and viscous flow in a cordierite glass-ceramic by using experimental growth rates and viscosity data. They concluded that the bond breaking and molecular reorientation required for crystallization is comparable to the atomic transport mechanism involved in viscous flow and hence viscosity data may be used to estimate crystal growth rates in glasses. pared the mechanical behaviour of cordieritemullite honeycombs with that of commercial cordierite foam with and without rubber encapsulation. While impact testing, the energy absorption of both the honeycomb and the foam increased upon rubber encapsulation. The rubber-encapsulated honeycomb had shown a substantial decrease in energy absorbed parallel to the channel walls, as opposed to an increase in the perpendicular direction.The foam absorbed less energy than the honeycomb. The critical stress decreased in the honeycomb but increased in foam upon rubber encapsulation.
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mal environments used for automobile pollution control as catalytic converters or as diesel particulate filters.Das et al [40] presented a comparative study on the thermal shock resistance of extruded cordierite honeycombs calculated by using CTE, MOE, MOR, etc.
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