Nanoparticles of SrTiO3 prepared by gel to crystallite conversion and their photocatalytic activity in the mineralization of phenol

Nanometre-sized powders of SrTiO3 were prepared at 70-100 degrees C by the wet-chemical method of gel to crystallite (G-C) conversion. The crystallite sizes obtained were in the range 5-13 nm, as estimated by transmission electron microscopy (TEM) studies. The photocatalytic activities of these powders in the mineralization of phenol were evaluated in comparison with Degussa P25 (TiO2). The maximum photocatalytic activity was observed for powders annealed in the range 1100-1300 degrees C. The optical spectra of the particle suspensions in water showed broadened absorption around the band gap region, together with the appearance of an absorption maximum in the UV region. The effect of inorganic oxidizing species as electron scavengers on the rate of the photocatalytic degradation of phenol was studied. The influence of bulk and surface defects, which participate in the charge transfer process during photocatalysis, was investigated systematically.

Processing map for hot working of powder

The constitutive flow behavior of a metal matrix composite (MMC) with 2124 aluminum containing 20 vol pct silicon carbide particulates under hot-working conditions in the temperature range of 300 °C to 550 °C and strain-rate range of 0.001 to 1 s-1 has been studied using hot compression testing. Processing maps depicting the variation of the efficiency of power dissipation given by [2m/(m + 1)] (wherem is the strain-rate sensitivity of flow stress) with temperature and strain rate have been established for the MMC as well as for the matrix material. The maps have been interpreted on the basis of the Dynamic Materials Model (DMM). [3] The MMC exhibited a domain of superplasticity in the temperature range of 450 °C to 550 °C and at strain rates less than 0.1 s-1. At 500 °C and 1 s-1 strain rate, the MMC undergoes dynamic recrystallization (DRX), resulting in a reconstitution of microstructure. In comparison with the map for the matrix material, the DRX domain occurred at a strain rate higher by three orders of magnitude. At temperatures lower than 400 °C, the MMC exhibited dynamic recovery, while at 550 °C and 1 s-1, cracking occurred at the prior particle boundaries (representing surfaces of the initial powder particles). The optimum temperature and strain-rate combination for billet conditioning of the MMC is 500 °C and 1 s-1, while secondary metalworking may be done in the super- plasticity domain. The MMC undergoes microstructural instability at temperatures lower than 400 °C and strain rates higher than 0.1 s-1.

Optimization of cold and warm workability in 304 stainless steel using instability maps

The deformation characteristics of stainless steel type AISI 3O4 under compression in the temperature range 20 degrees C to 600 degrees C and strain-rate range 0.001 to 100 s(-1) have been studied with a view to characterizing the flow instabilities occurring in the microstructure. At strain rates less than 5 s(-1), 304 stainless steel exhibits flow localization, whereas dynamic strain aging occurs at intermediate temperatures and below 0.5 s(-1). At room temperatures and strain rates less than 10 s(-1), martensite formation is observed. To avoid the preceding microstructural instabilities, cold and warm working should be carried out at strain rates greater than 5 s(-1). 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 preceding instability features.

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Quasicrystals, crystals and multiple twins in rapidly solidified Al-Cr-Si, Al-Mn-Si and Al-Mn-Cr-Si alloys

The coexistence of quasicrystals and rational approximant structures (RAS) has been observed in melt-spun Al80Cr14Si6, Al80Mn14Si6 and Al75Mn10Cr5Si10 alloys. The presence of a b.c.c. alpha-AlMnSi phase in Al-Mn-Si and alpha-AlMnSi(Cr) phase in Al-Mn-Cr-Si has been seen. A multiple twinning around an irrational axis of the RAS has been reported in an aggregate of fine size cubic crystallites in all three alloys. Selected area diffraction patterns show that the crystalline aggregate symmetry is linked to the icosahedral point group symmetry (m35). Various ways of expressing the twin relationship in the cubic crystalline aggregates have been discussed. The thermal stability of the icosahedral phase at high temperatures reveals that the icosahedral phase in Al-Mn-Si and Al-Mn-Cr-Si alloys transforms to alpha-AlMnSi at temperatures of 690 and 670 K, respectively. In Al-Cr-Si alloy, heating to a high temperature (615 K) leads to the transformation of the icosahedral phase into a new metastable phase having an ordered cubic structure equivalent to alpha-AlMnSi. The occurrence of multiple twinning leading to icosahedral symmetry in the as-spun Al-Cr-Si alloy is presumably due to this metastable phase. Copyright (C) 1996 Acta Metallurgica Inc.

Repeated drop weight impacts and post-impact ILSS tests on glass-epoxy composite

E glass epoxy laminates of thicknesses in the range 2-5 mm were subjected to repeated impacts. For each thickness the number of hits to cause tup penetration was determined and the value of this number was higher the larger the thickness of the laminate tested. The C-scan, before and after impact, was done to obtain information regarding flaw distribution. Short beam shear test samples were made from locations at fixed distances from impact point and tested. The samples closer to the zone of impact showed lower strength values. Scanning fractography revealed shear deformation features for these samples and brittle fracture features for the region near the zone of impact.

Role of bacterial growth conditions and adhesion in the bioleaching of chalcopyrite by Thiobacillus ferrooxidans

The role of growth conditions and adhesion of Thiobacillus ferrooxidans on the leaching of chalcopyrite was investigated. Thiobacillus ferrooxidans grown on sulfur, thiosulfate and ferrous ion substrates was used in this comparative study. Growth on sulfur, a solid substrate, requires bacterial adhesion unlike that required in the presence of soluble thiosulfate and ferrous ion in a mineral-salts medium. Solid substrate-grown cells showed higher rates of leaching than those grown in liquid media. An initial lag period noticed during leaching by solution-grown cells was absent when solid substrate-grown cells were used. Such a behavior is attributed to the presence of an inducible proteinaceous cell-surface appendage on the sulfur-grown cells. This appendage aids in bacterial adhesion onto the mineral surfaces. Such an appendage is absent in solution-grown cells, as substantiated by electrophoretic measurements. The importance of bacterial adhesion and the direct mechanism in leaching by Thiobacillus ferrooxidans are demonstrated.

Role of zirconium addition on stability of UAl3 phase in Al-U system

The microstructural changes of Al-22 wt%U and Al-46 wt%U alloys containing 3 wt% Zr were investigated after heat treatment at 620 degrees C for 1 to 45 days, Though it is reported that addition of similar to 3 wt% Zr stabilizes the (U,Zr)Al-3 phase at room temperature, the present investigation shows that the (U,Zr)Al-3 phase is not stable but slowly transforms to the U0.9Al4 phase, The high temperature creep curves generated for these ternary alloys showed a wavy pattern which also suggests that the (U,Zr)Al-3 phase is not stable.

Derivation and consistency of the partial functions of the ternary system involving interaction coefficients

The logarithm of activity coefficients of the components of the ternary system is derived based on the Maclaurin infinite series, which is expressed in terms of the integral property of the system and subjected to appropriate boundary conditions. The derivation of the functions involves extensive summation of various infinite series pertaining to the first-order interaction coefficients that have been shown completely to remove any truncational error. Since the conventional equations involving interaction coefficients are internally inconsistent, a consistent form of the partial functions is developed in the article using the technique just described. The thermodynamic consistency of the functions based on the Maxwell and the Gibbs-Duhem relations has been established. The derived values of the logarithmic activity coefficients of the components have been found to be in agreement with the thermodynamic data of the Fe-Cr-Ni system at 1873 K and have been found to be independent of the compositional paths.

Sintering of beta titanium: Role of dislocation pipe diffusion

Sintering of titanium in its high temperature beta phase was studied by isothermal dilatometry. The sintering shrinkage y did not follow the normal time exponent type of behaviour, instead being described by the equation y = Kt(m)/[1-(A+Bt)(2)], where m = 1.93 +/- 0.07, with an activation energy of 62-90 kJ mol(-1). A detailed analysis of these results, based on the 'anomalous' diffusion behaviour reported for beta titanium, is carried out. It is shown that the generation of a high density of dislocations during the alpha --> beta phase transformation, coupled with sluggish recovery at the sintering necks, enables sintering mass transport by pipe diffusion through dislocation cores from sources of matter within the particles to become dominant.

Design of solid electrolytes for use with dissimilar gas electrodes

The design of a solid electrolyte that permits the use of dissimilar gas electrodes in an electrochemical cell is presented. It consists of a functionally gradient material with spatial variation in composition. The activity of the conducting ion is fixed at each electrode using different gas species. The system chosen for demonstrating the concept consists of a solid solution between K2CO3 and K2SO4. The composition of the solid solution varies from pure K2CO3 in contact with a CO2 + O2 gas mixture at one electrode to pure K2SO4 exposed to a mixture of SO3 + SO2 + O2 at the other. Two types of composition profiles are studied, one with monotonic variation in composition and the other with extrema. The e.m.f. of the cells is studied as a function of temperature and composition of the gas mixture at each electrode. The results indicate that the e.m.f. is determined primarily by the difference in the chemical potential of potassium at the two electrodes. The diffusion potential caused by ionic concentration gradients in the electrolyte appears to be negligible when the corresponding ionic transport numbers are insignificant. Studies on the response characteristics of the cell based on the gradient electrolyte indicate that the nature of the variation in composition of the electrolyte has only a minor effect on the time evolution of e.m.f. The gradient solid electrolytes have potential application in multielement galvanic sensors at high temperatures.

Determination of the Gibbs energy of diamond using a solid state cell

he chemical potential of carbon in diamond, relative to its value in graphite, has been directly determined using a solid state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The cell can be represented as Pt, C(graphite) + CaC2 + CaF2double vertical barCaF2double vertical barCaF2 + CaC2 + C(diamond), Pt The reversible emf of this cell is directly related by the Nernst equation to the Gibbs free energy change for the conversion of diamond to graphite. The difference in the chemical potential of carbon in the two crystal structures varies linearly with temperature in the range 940 to 1260 K ?C(diamond) ? ?C(graphite) = 1100 + 4.64T (±50) J mol?1 On the average, the values given by the equation are 320 J mol?1 less positive than the currently accepted ones based on calorimetric studies. The difference is primarily in the enthalpy term.

Differences in the glass-forming ability of rapidly solidified and mechanically alloyed Ti-Ni-Cu alloys

Melt spinning of Ti50Ni50 ? xCux (x = 10, 25, 40) alloys showed that the glass-forming ability is good for Cu-rich compositions and poor for Ni-rich compositions. The results of mechanical alloying experiments in the same system showed a reverse trend as far as the glass-forming ability is concerned. These contradictory results are explained in the light of thermodynamic and kinetic considerations. Crystallization results of the melt spun alloys are also presented.

Representation of thermodynamic properties of ternary systems and its application to the system silver-gold-copper at 1350 K

The article presents a generalized analytical expression for description of the integral excess Gibbs free energy of mixing of a ternary system. Twelve constants of the equation are assessed by the least mean squares regressional analysis of the experimental integral excess data of the constituent binaries; three ternary parameters are evaluated by a regressional analysis based on the partial experimental data of a component of the ternary system. The assessed values of the ternary parameters describe the nature of the ternary interaction in the system. Activities and isoactivities of the components in the Ag-Au-Cu system at 1350 K are calculated and found to be in good agreement with the experimental data. This analytical treatment is particularly useful to ternary systems where the thermodynamic data are available from different sources.

Study of fracture features in foam bearing glass epoxy composites subjected to repeated impacts

The paper reports the failure features observed in low mass repeatedly (pendulum) impacted glass epoxy composites with and without the mid section having either 2-layers or 3-layers of flexible foam. Features such as through width and inclined cracks as well as adhering of foam observed in the experiments are explained. The significance of the foam material in modifying the impact response of the composite is stressed.