Combustion synthesis and properties of fine-particle rare-earth-metal zirconates, Ln2Zr2O7

Fine-particle rare-earth-metal zirconates, Ln2Zr2O7, where Ln = La, Ce, Pr, Nd, Sm, Gd and Dy having the pyrochlore structure have been prepared using a novel combustion process. The process employs aqueous solutions of the corresponding rare-earth-metal nitrate, zirconium nitrate and carbohydrazide/urea in the required molar ratio. When the solution is rapidly heated to 350–500 °C it boils, foams and burns autocatalytically to yield voluminous oxides. The formation of single-phase Ln2Zr2O7 has been confirmed by powder X-ray diffraction, infrared and fluorescence spectroscopy. The solid combustion products are fine, having surface areas in the range 6–20 m2 g–1. The cold-pressed Pr2Zr2O7 compact when sintered at 1500 °C, 4 h in air, achieved 99% theoretical density.

Continuity of plastic strain rate in stress relaxation tests

Stress relaxation testing is often utilised for determining whether athermal straining contributes to plastic flow; if plastic strain rate is continuous across the transition from tension to relaxation then plastic strain is fully thermally activated. This method was applied to an aged type 316 stainless steel tested in the temperature range 973–1123 K and to a high purity Al in the recrystallised annealed condition tested in the temperature range 274–417 K. The results indicated that plastic strain is thermally activated in these materials at these corresponding test temperatures. For Al, because of its high strain rate sensitivity, it was necessary to adopt a back extrapolation procedure to correct for the finite period that the crosshead requires to decelerate from the constant speed during tension to a dead stop for stress relaxation.

Criteria for prediction of flow instabilities and microstructural manifestations during warm working of AISI 304L stainless steel

The deformation characteristics of 304L stainless steel in compression in the temperature range 20–700°C and strain rate range 0·001–100 s−1 have been studied with the aim of characterising the .flow instabilities occurring in the microstructure. At higher temperatures and strain rates the stainless steel exhibits flow localisation, whereas at temperatures below 500°C and strain rates lower than 0·1 s−1 the flow instabilities are due to dynamic strain aging. Strain induced martensite formation is responsible for the flow instabilities at room temperature and low strain rates (0·01 s−1). In view of the occurrence of these instabilities, cold working is preferable to warm working to achieve dimensional tolerance and reproducible properties in the product. Among the different criteria tested to explain the occurrence of instabilities, the continuum criterion, developed on the basis of the principles of maximum rate of entropy production and separability of the dissipation function, predicts accurately all the above instability features.

Electron-beam weld microstructures and properties of aluminium-lithium alloy 8090

Lithium-containing aluminium alloys are of considerable current interest in the aerospace and aircraft industries because lithium additions to aluminium improve the modulus and decrease the density compared to conventional aluminium alloys. Few commercial aluminium-lithium alloys have emerged for use in the aerospace industry. One such candidate is 8090, a precipitation-hardenable Al-Li-Cu-Mg alloy. The influence of electron-beam welding on the microstructure and mechanical properties of alloy 8090 material has been evaluated through microscopical observations and mechanical tests. Microscopic observations of the electronbeam welds revealed an absence of microporosity and hot cracking, but revealed presence of microporosity in the transverse section of the weld. Mechanical tests revealed the electronbeam weld to have lower strength, elongation and joint efficiency. A change in microscopic fracture mode was observed for the welded material when compared to the unwelded counterpart. An attempt is made to rationalize the behaviour in terms of competing mechanistic effects involving the grain structure of the material, the role of matrix deformation characteristics, grain-boundary chemistry and grain-boundary failure.

Intercalation of n-alkylamines in iron thiohypophosphate (FePS3)

The intercalation of linear alkylamines (C1-C4) in the two-dimensional (2D) Ising antiferromagnet, FePS3, has been investigated. Intercalation proceeds with a dilation of the interlayer distance. The expansion (approximately 3.8 angstrom) is the same for all four amine molecules, suggesting that they are oriented flat with respect to the layers. From an analysis of the products of deintercalation, it is concluded that the intercalated species are the alkylammonium cations and neutral amine molecules. The intercalated compounds are highly moisture sensitive, as reflected in the chemical nature of the intercalated species. Charge neutrality of the lattice after intercalation is preserved by the loss of Fe2+ ions from the lattice. These Fe2+ ions are further oxidized to form superparamagnetic Fe2O3 clusters, as confirmed by Mossbauer spectra and magnetic measurements. This was further corroborated by in situ EPR studies. The Fe-57 Mossbauer spectra of the intercalated compounds showed evidence for two species other than Fe2O3. On the basis of the observed isomer shifts and quadrupole splittings, they have been assigned to Fe2+ in an environment similar to that in FePS3 and in a distorted FePS3 environment. The temperature and field dependence of the magnetic susceptibility of single crystals of the amine-intercalated FePS3 have been measured. Their magnetic behavior shows many of the features expected of a 2D Ising antiferromagnet with random defects, Fe1-xPS3, in agreement with the mechanism of intercalation.

Numerical and experimental study of the thermal behaviour of coining and upsetting processes

A numerical simulation technique has been employed to study the thermal behavior of hot-forging type forming processes. Experiments on the coining and upsetting of an aluminum billet were conducted to validate the numerical predictions. Typical forming conditions for both the coining and upsetting processes were then studied in detail. an electrical analogy scheme was used to determine the thermal contact resistance. This scheme can conviniently provide the interface characteristics for typical processing conditions, which normally involve high pressures and temperatures. A single forging cycle was first considered, and then a batch of twenty-five forgings was studied. Each forging cycle includes the billet mounting, ascent, loading, dwelling, unloading, descent, and billet removal stages. The temperature distribution in the first forging to be formed is found to be significantly different from that at the end of the batch. In industry, forging is essentially a batch operation. The influence of forming speed and reduction on thermal characteristics was investigated also. The variations that can occur in the process design by considering differences in temperature characteristics are discussed also.

Phase relations and thermodynamic properties of condensed phases in the system calcium-copper-oxygen

The isothermal sections of the phase diagram for the system Ca-Cu-0 at 1073 and 1223 K have been determined. Several compositions in the ternary system were quenched after equilibration, and the phases present were identified by optical microscopy, X-ray diffraction, and electron probe microanalysis. Two ternary compounds Ca2CuO3 and Cao.8&uO1.9s were identified at 1073 K. However, only Ca2CuO3 was found to be stable at 1223 K. The thermodynamic properties of the two ternary compounds were determined using solid-state cells incorporating either an oxide or a fluoride solid electrolyte. The results for both types of cells were internally consistent. The compound C ~ O . ~ & U Ow~h.i~ch~ c, a n also be represented as Ca15Cu18035h, as been identified in an earlier investigation as Cao.828CuOz. Using a novel variation of the galvanic cell technique, in which the emf of a cell incorporating a fluoride electrolyte is measured as a function of the oxygen potential of the gas phase in equilibrium with the condensed phase electrodes, it has been confirmed that the compound Cao.828CuO1.93 (Ca15Cu18035d) oes not have significant oxygen nonstoichiometry. Phase relations have been deduced from the thermodynamic data as a function of the partial pressure of oxygen for the system Ca-Cu-0 at 873, 1073, and 1223 K.

Phase relations in the systems Cu–O–R2O3(R = Tm, Lu) and Gibbs energies of formation of Cu2R2O5 compounds

The phase relations in the systems Cu–O–R2O3(R = Tm, Lu) have been determined at 1273 K by X-ray diffraction, optical microscopy and electron probe microanalysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only ternary compounds of the type Cu2R2O5 were found to be stable. The standard Gibbs energies of formation of the compounds have been measured using solid-state galvanic cells of the type, Pt|Cu2O + Cu2R2O5+ R2O3‖(Y2O3)ZrO2‖CuO + Cu2O‖Pt in the temperature range 950–1325 K. The standard Gibbs energy changes associated with the formation of Cu2R2O5 compounds from their binary component oxides are: 2CuO(s)+ Tm2O3(s)→Cu2Tm2O5(s), ΔG°=(10400 – 14.0 T/K)± 100 J mol–1, 2CuO(s)+ Lu2O3(s)→Cu2Lu2O5(s), ΔG°=(10210 – 14.4 T/K)± 100 J mol–1 Since the formation is endothermic, the compounds become thermodynamically unstable with respect to component oxides at low temperatures, Cu2Tm2O5 below 743 K and Cu2Lu2O5 below 709 K. When the chemical potential of oxygen over the Cu2R2O5 compounds is lowered, they decompose according to the reaction, 2Cu2R2O5(s)→2R2O3(s)+ 2Cu2O(s)+ O2(g) The equilibrium oxygen potential corresponding to this reaction is obtained from the emf. Oxygen potential diagrams for the Cu–O–R2O3 systems at 1273 K are presented.

Role of Gypsum in the Strength Development of Fly Ashes with Lime

The strength of fly ash mixture often needs to be enhanced for its better utilization in geotechnical and environmental applications. Many fly ashes often improve their strength with lime but may not meet the requirements. Gypsum, which reduces the lime leachability, further improves the strength. An attempt is made in this paper to study the effect of gypsum on the strength development of two Class F fly ashes with different lime contents after curing them for different periods. The sustainability of improved strength has been examined after soaking the cured specimens in water and with different leachates containing heavy-metal ions. The strength of both the fly ashes investigated improved markedly up to a particular amount of the lime content, which can be taken as optimum lime content, and thereafter the improvement is gradual. The improvement in strength at higher lime contents continues for a longer period (even up to 180 days). Gypsum accelerates the gain in strength for lime-stabilized fly ashes, particularly in the initial curing periods at about optimum lime content. At high lime contents gypsum attributes very high strength after curing for long periods mainly due to the alteration of fly ash lime reaction compounds. Gypsum not only improves the reduction in the loss of strength due to soaking even at low curing periods but also improves the durability of stabilized fly ashes due to repeated cycles of wetting and drying.