Nanocrystalline magnetite powders were synthesized by an electrocoagulation technique, in which an electric current was passed across two plate electrodes of carbon steel immersed in NaCl(aq) electrolyte, and the microstructure of the oxide powder was found to evolve in roughly three stages. The first stage involves formation and growth of severely defective colloidal crystallites. This is followed by agglomeration among the oxide crystallites to form mesoporous agglomerates containing predominantly inter-crystallite pores, and the average crystallite size was found to reach a plateau. Finally, coarsening of the crystallites within the agglomerates leads to another rapid increase in crystallite size and reduction in pore opening. The synthesized powders typically showed a saturation magnetization of ∼75 emu/g and a coercivity Hc of ∼118 Oe. A mechanism involving competition between nucleation and growth of free colloids and coarsening of the skeletal framework was proposed to explain the temporary level-off in crystallite size during the synthesis.

Mesoporous crystalline SnO2 was synthesized by using templating process with cetyltrimethylammonium bromide as the template, combined with a pretreatment process of hexamethyldisilazane vapor prior to thermal crystallization. The combined process resulted in crystalline SnO2 exhibiting large pore volumes and surface areas that cannot be achieved by either of the processes alone, or by the conventional sol-gel process. Fully crystallized SnO2 powder with a pore volume of approximately 0.2 cc/g, a surface area of 220 m2/g, and mesopores mainly of 5 nm in diameter were obtained after heat treatment at 500°C.

The thermodynamic stability of tetragonal (t-) ZrO2 nanocrystallites below the bulk stability temperature 1200 °C was studied through specially synthesized crystallites that exhibited an extremely slow coarsening rate. The nanocrystallites were mechanically transformed to the monoclinic (m-) structure, and, because the crystallite size was kept below approximately 20 nm, the t-structure was completely recovered solely by thermal treatments between 900 and 1100 °C. These results gave strong evidence to the notion that, for sufficiently small crystallite size, nanocrystalline t-ZrO2 is not just kinetically metastable but can be truly thermodynamically more stable than the mpolymorph in air below 1200 °C.

SnO crystallites having a size ranging 0.1–0.2 μm were synthesized by a hydrothermal process, which consisted of prolonged solution aging under pH = 1.0, followed by hydrothermal treatment under pH = 9 to 10 at 75–95 °C. Oxidation of Sn+2 to Sn+4 during the hydrothermal stage was effectively inhibited by increasing the solution-aging time. This was attributed to the formation, upon aging, of polymeric hydrous SnO colloids, which are more oxidation resistant than aquo-hydroxo tin complex monomers. For solutions with a sufficiently long (≥240 h) aging time, the SnO yield increased with increasing pH and temperature during the hydrothermal treatment.

A sol-gel process for preparing SnO2 monolith of high specific surface area and transparency from chloride solution is described. Without introducing any alkaline precipitating reagent to induce condensation, this new process employs tin chloride (or its hydrate), water, and, optionally, alcohols as the only process reagents. Spontaneous solution-to-sol and sol-to-gel transitions take place upon mixing these reagents under appropriate conditions, and the entire transition processes are carried out under acidic conditions (typically pH ≤ 4.0). The rate of condensation has been found to increase with decreasing SnCl4 concentration, which corresponds to decreasing solution acidity, and with increasing temperature. For fixed starting salt concentration and temperature, there exists an optimum amount of ethanol addition for the fastest condensation. Good performance of thus derived SnO2 monolith has been demonstrated in two applications, including catalytic oxidation and solid-state gas-sensing for carbon monoxide.

The stability of YBa2Cu3O7−x (the 123 compound) in contact with silver (Ag) at temperatures below 900 °C was investigated by conducting SEM and EDX analyses on 123 agglomerates that were enclosed in a dense Ag matrix and subjected to various thermal treatments. The stability of the 123 agglomerates was found to depend heavily on the oxygen content in the Ag matrix. In the case of insufficient oxygen content in Ag, the 123 agglomerates, which were as large as 150 μm thick, decomposed readily at temperatures above 500 °C. The complete decomposition process can be summarized as continuous extraction of Ba from the 123 oxide into the surrounding Ag matrix and is proposed to be driven by high mutual solubilities between Ag and Ba under the oxygen-lean condition. Prolonged preoxygenation of the (123 + Ag) mixture powders at temperatures above 400 °C prevents the occurrence of 123 decomposition in compacted samples during subsequent heat treatment, suggesting that the critical oxygen content in Ag for stabilizing the 123 compound to be no higher than 10−3 at. % (the oxygen saturation solubility at 400 °C). The findings may have implications for the processing of other Ba-containing high-Tc superconducting oxides as well.

The kinetics of the solid-state reaction Y2BaCuO5 + 3BaCuO2 + 2CuO ⇉ 2YBa2Cu3O6.5−x + xO2 was studied by using x-ray diffractometric and thermogravimetric analyses. Both analyses established that the reaction was well described by the kinetic equation: 1 − 3(1 − F)2/3 + 2(1 − F) = k0 exp(− E/RT)t, where F is the fractional conversion of a calcined powder, E is 520 kcal/molc and, for a rcactant mixture with an average particle size of 3 μm, k0 is 2.03 ⊠ 1092 min−1. An unreacted-core shrinking model was proposed to obtain the particle-size dependence of the reaction, and predicted that the pre-exponential constant k0 changed with reactant particle size by k0 = 2.03 ⊠ 1092(3/d)2 exp(4/d − 4/3), where d is the average reactant particle size in μm.

The kinetics of the reactions that lead to the formation of YBa2Cu3O7−x was investigated starting from various powder mixtures containing different reactants as sources of Ba, Cu, and Y (BaCO3, BaO, CuO, Y2O3. Y2Cu3O5. and BaCuO2). These powders were calcined at 940 °C for various time intervals. Quantitative x-ray analysis was used to determine the relative amounts of the compounds present in the calcined powders. When BaCO3 was used as the source of barium, long calcination times were required to obtain the single phased YBa2Cu3O7−x because of the slow decomposition of BaCO3. This leads to large particles and broad particle size distributions and hence to a lower density of the sintered superconducting pellets. Procedures to attain high density superconducting material are identified on the basis of the kinetic studies. Each of them isolates the slow reaction in a first step and prepares the superconducting material via a rapid reaction in a second step. The kinetic studies reveal the reaction mechanisms that were followed in different cases.

New powder synthesis Methods have been developed for preparing the single-phase T12CaBa2Cu2O8 (the 2122 coapound) and T12CaBa2Cu3O10 (the 2223 coapound) powders froa stoichioaetric reactant mixtures. The 2122 coapound was prepared froa a stoichioaetric Mixture of T12O3, CuO, and CaBa2CuO4, while the 2223 coapound was prepared froa the same aixture but with additional CaO and CuO to Batch the correct (T1:Ca:Ba:Cu=2:2:2:3) stoichioaetry. The single-phase 2122 saaples with Tc above 110 K were obtained by using one-step calcination at 830°C, while the 2223 saaples with Tc ranging between 115 and 120 K were obtained by employing a first calcination at 830°C for 5 hrs and a second calcination at 870°C. Powder aelting, which is strongly associated with the conventional aethods, was significantly suppressed in the new aethods.