Synthesis of lithium aluminate,mullite and coloured zirconia by a combustion process

Also with the Department of Agronomy.     

Anionic Clays as Potential Slow-Release Fertilizers: Nitrate Ion Exchange

Several nitrate containing anionic clays were synthesized at different temperatures and the kinetics of NO₃ ^– release were determined to test their suitability as slow-release N fertilizers. A sample (Mg:Al = 2:1) synthesized at 60°C with smaller particle size released 75, 86 and 100% of its NO₃ ^– in 1, 3 and 7 days, respectively when equilibrated with a simulated soil solution. On the other hand, the 175°C/2 hrs sample with larger particle size released 65, 77 and 84% of its nitrate in 1, 3 and 7 days, respectively. Another anionic clay (synthesized at 175°C/24 hrs) of higher charge density (Mg:Al = 2:1) containing NO₃ ^– was equilibrated with a 0.012 N NaCl or Na₂CO₃ to test the role of different anions in releasing the NO₃ ^– anion from the interlayers. The results showed that Cl^– released more NO₃ ^– than did CO₃ ^2– from this anionic clay after all the treatment times probably as a result of the CO₃ ^2– anion blocking the release of NO₃ ^– from the interior of the crystals. When a lower charge density (Mg:Al = 3:1) sample (synthesized at 175°C/48 hrs) was equilibrated with 0.02N solution of anions the release of nitrate was as follows: Cl^– < F^– < SO₄ ⁼ CO₃ ^2–. These results suggest that the divalent SO₄ ⁼ and CO₃ ^2– anions are more effective in the release of NO₃ ^– from this lower charge density anionic clay. Time-resolved structural analysis of NO₃ ^– exchange with CO₃ ^2– in the above anionic clay using synchrotron x-ray diffraction showed that ion exchange is rapid because of small crystal size and lower charge density. Thus the release of NO₃ ^– from anionic clays is an interplay among the type of anions present in soil solution, their concentration, pH of soil solution, the charge density and crystal size of anionic clay etc.     

Porous mullite ceramics through diphasic gels of large boehmite and small silica particles

Mullite formation process has been studied in stoichiometric mullite (3Al₂O₃·2SiO₂) diphasic gel containing large boehmite (1 m) and small silica (10 nm) particles. It has been found that initial mullitization did not take place inside the silica phase (cristobalite), but took place in the defect -alumina phase. -alumina was stabilized by silica when the temperature was below 1350°C. At temperatures above 1350°C, mullite crystallized directly. It was suggested that silica diffused into the pores (<1.8 nm) of -alumina and prevented the collapse of -alumina pore structure. On the other hand, when silica was not present, the pore structure of -alumina collapsed and -alumina crystallized at 1100°C. Porous mullite ceramics were obtained by using special diphasic gels containing large boehmite and small silica particles.     

Sequestration of Cesium and Strontium by Tobermorite Synthesized from Fly Ashes

Tobermorites were synthesized from oxides and from fly ashes under mild hydrothermal conditions. The bulk compositions of the ash-based formulations were adjusted to give the same [Ca]/[Si + Al] ratio as for the oxides. Selective Cs and Sr exchange with these tobermorites was measured. Compared to those prepared from the oxides and from class C fly ash, the tobermorites obtained from class F fly ash exhibited superior Cs and Sr selective properties. This is apparently a result of more extensive Al incorporation with class F fly ash. For example, tobermorite synthesized from class F fly ash exhibited a cesium K _d (mL/g) of 3826 while those prepared from oxides and from class C fly ash showed K _d values of 1112 and 796, respectively, under the same conditions. These results suggest that fly ash waste materials can be converted into tobermorite, which can serve as a resource in the separation, immobilization, and disposal of radioactive species such as Cs and Sr.     

Nanocomposite route to the stabilization of porous ϑ-alumina

Stabilization of -alumina phase by silica was studied in nanocomposite (diphasic) alumina-silica gels by XRD and BET surface areas measurements. Five wt.% of silica (22 nm particles) increased the crystallization temperature of to -alumina by about 100°C from boehmite (10 nm particles) derived alumina. Stabilization of -alumina was caused by the formation of intimate contact (Al-O-Si) between components by diffusion of silica into the defect alumina structure.Also with the Department of Agronomy.     

Microwave-Hydrothermal Processing of BiFeO3 and CsAl2PO6

Microwave-hydrothermal (M-H) processing was compared with conventional-hydrothermal (C-H) processing in the crystallization of BiFeO₃ and CsAl₂PO₆ phases. The presence of the microwave field led to accelerated kinetics of the crystallization of both these phases as detected by powder X-ray diffraction. The acceleration of reaction rates under microwave field is expected to lead to energy savings during ceramic processing.     

Seeding effects on crystallization temperatures of cordierite glass powder

The role of solid state epitaxy in the crystallization of nanocomposite cordierite glass to glass ceramic was investigated. The use of isostructural (-cordierite) seeds in cordierite glass led to a lowering in the crystallization temperature to form glass ceramic by about 50 °C compared to the unseeded glass. The use of non-isostructural seeds such as ZrO₂ and TiO₂ did not lower the crystallization temperature of cordierite glass to glass ceramic, and in the case of the TiO₂-seeded glass the crystallization temperature increased by about 50 °C compared to the unseeded-cordierite glass. The lowering in crystallization temperature by-cordierite seeding can be attributed to the nucleation and epitaxial growth mechanism.     

Preparation of La2Zr2O7 by Sol—Gel Route

The La₂Zr₂O₇ phase was prepared from metal acetylacetonates by a sol—gel route without any intermediate phase formation. X-ray peaks appeared at a temperature as low as 500°C at the positions expected for La₂Zr₂O₇, although they were broad. The crystal structure of La₂Zr₂O₇ was found to be of the fluorite type below 900°C and of thepyrochlore type above 1000°C. The substitution of a small amount of Eu for La was carried out to investigate the crystal structure from the viewpoint of fluorescence, and these results confirmed the formation of fluorite type La₂Zr₂O₇ below 900°C.