Processing maps for hot working of Cu-Ni-Zn alloys. Part I - Alpha-nickel silver

The constitutive behaviour of agr — nickel silver in the temperature range 700–950 °C and strain rate range 0.001–100 s–1 was characterized with the help of a processing map generated on the basis of the principles of the ldquodynamic materials modelrdquo of Prasadet al Using the flow stress data, processing maps showing the variation of the efficiency of power dissipation (given by 2m/(m+1) wherem is the strain-rate sensitivity) with temperature and strain rate were obtained, agr-nickel silver exhibits a single domain at temperatures greater than 750 °C and at strain rates lower than 1s–1, with a maximum efficiency of 38% occurring at about 950 °C and at a strain rate of 0.1 s–1. In the domain the material undergoes dynamic recrystallization (DRX). On the basis of a model, it is shown that the DRX is controlled by the rate of interface formation (nucleation) which depends on the diffusion-controlled process of thermal recovery by climb. At high strain rates (10 and 100s–1) the material undergoes microstructural instabilities, the manifestations of which are in the form of adiabatic shear bands and strain markings.

Can Dufour's gland compounds honestly signal fertility in the primitively eusocial wasp Ropalidia marginata?

Unlike queens of typical primitively eusocial species, Ropalidia marginata queens are docile and non-interactive, and hence cannot be using dominance to maintain their status. It appears that the queen maintains reproductive monopoly through a pheromone, of which the Dufour's gland is at least one source. Here, we reconfirm earlier results showing that queens and workers can be correctly classified on a discriminant function using the compositions of their respective Dufour's glands, and also demonstrate consistent queen-worker differences based on categories of compounds and on single compounds also in some cases. Since the queen pheromone is expected to be an honest signal of the fecundity of a queen, we investigate the correlation of Dufour's gland compounds with ovarian activation of queens. Our study shows that Dufour's gland compounds in R. marginata correlate with the state of ovarian activation of queens, suggesting that such compounds may portray the fecundity of a queen, and may indeed function as honest signals of fertility.

Edge-sharing bioctahedral diruthenium(III) complexes containing methoxy and carboxylate bridges:x-ray structures, redox behavior, and core stability

Edge-sharing bioctahedral (ESBO) complexes [Ru-2(OMe)(O2CC6H4-p-X)3(1-MeIm)(4)](ClO4)2 (X = OMe (1a), Me (1b)) and [Ru-2(O2CC6H4-P-X)(4)(1-MeIm)(4)](ClO4)(2) (X = OMe (2a), Me (2b)) are prepared by reacting Ru2Cl(O(2)CR)(4) with 1-methylimidazole (1-MeIm) in methanol followed by treatment with NaClO4. Complex 2a and the PF6- salt (1a') of 1a have been structurally characterized. Crystal data for 1a.1.5MeCN. 0.5Et(2)O: triclinic, P (1) over bar, a = 13.125(2) Angstrom, b = 15.529(3) Angstrom, c 17.314(5) Angstrom, a; 67.03(2)degrees, beta 68.05(2)degrees, gamma = 81.38(1)degrees, V 3014(1) Angstrom(3), Z = 2. Crystal data for 2a: triclinic, P (1) over bar, a 8.950(1) Angstrom, b = 12.089(3) Angstrom, c = 13.735(3) Angstrom, alpha 81.09(2)degrees, beta = 72.27(1)degrees, gamma = 83.15(2)degrees, V = 1394(1) Angstrom(3), Z = 1. The complexes consist of a diruthenium(III) unit held by two monoatomic and two three-atom bridging ligands. The 1-MeIm ligands are at the terminal sites of the [Ru-2(mu-L)(eta(1):mu-O(2)CR)(eta(1):eta(1):mu-O(2)CR)(2)](2+) core having a Ru-Ru single bond (L = OMe or eta(1)-O(2)CR). The Ru-Ru distance and the Ru-O-Ru angle in the core of 1a' and 2a are 2.49 Angstrom and similar to 76 degrees. The complexes undergo one-electron oxidation and reduction processes in MeCN-0.1 M TBAP to form mixed-valence diruthenium species with Ru-Ru bonds of orders 1.5 and 0.5, respectively.

Gibbs energy of formation of orthorhombic CaZrO3

The Gibbs free energy of formation of the orthorhombic form of CaZrO3(o) from monoclinic ZrO2(m) and periclase CaO(p) has been determined as a function of temperature in the range 950-1225 K, using an electrochemical cell incorporating single-crystal CaF2 as the solid electrolyte. The results are corrected for the small solid solubility of CaO in ZrO2. For the reaction, ZrO2(m) + CaO(p) --> CaZrO3(o), DELTAG(phi) = -31590 -13.9T(+/- 180) J mol-1. The ''second-law'' enthalpy of formation of CaZrO3 obtained from the results of this study at a mean temperature of 1090 K is in excellent agreement with the high-temperature solution calorimetric measurements of Muromachi and Navrotsky at 1068 K (J. Solid State Chem., 72 (1988) 244), and the average value of the bomb and acid solution calorimetric studies of Lvova and Feodosev (Zh. Fiz. Khim., 38 (1964) 28), Korneev et al. (Izv. Akad. Nauk SSSR, Neorg. Mater., 7 (1971) 886) and Brown and Bennington (Thermochim. Acta, 106 (1986) 183). The standard entropy of CaZrO3(o) at 298.15 K from the free energy data is 96.4 (+/- 3.5) J K-1 mol-1. The results of this study are discussed in comparison with high-temperture e.m.f. measurements reported in the literature on cubic zirconia solid solutions.

Microstructural control in hot working of IN-718 superalloy using processing map

The hot-working characteristics of IN-718 are studied in the temperature range 900 °C to 1200 °C and strain rate range 0.001 to 100 s−1 using hot compression tests. Processing maps for hot working are developed on the basis of the strain-rate sensitivity variations with temperature and strain rate and interpreted using a dynamic materials model. The map exhibits two domains of dynamic recrystallization (DRX): one occurring at 950 °C and 0.001 s−1 with an efficiency of power dissipation of 37 pct and the other at 1200 °C and 0.1 s−1 with an efficiency of 40 pct. Dynamic recrystallization in the former domain is nucleated by the δ(Ni3Nb) precipitates and results in fine-grained microstructure. In the high-temperature DRX domain, carbides dissolve in the matrix and make interstitial carbon atoms available for increasing the rate of dislocation generation for DRX nucleation. It is recommended that IN-718 may be hot-forged initially at 1200 °C and 0.1 s−1 and finish-forged at 950 °C and 0.001 s−1 so that fine-grained structure may be achieved. The available forging practice validates these results from processing maps. At temperatures lower than 1000 °C and strain rates higher than 1 s−1 the material exhibits adiabatic shear bands. Also, at temperatures higher than 1150°C and strain rates more than 1s−1, IN-718 exhibits intercrystalline cracking. Both these regimes may be avoided in hotworking IN-718.

Modified Crack Closure Integral (MCCI) For 3-D Problems Using 20-Noded Brick Elements

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Hot deformation characteristics of INCONEL alloy MA 754 and development of a processing map

The characteristics of hot deformation of INCONEL alloy MA 754 have been studied processing maps obtained on the basis of flow stress data generated in compression in the temperature range 700-degrees-C to 1150-degrees-C and strain rate range 0.001 to 100 s-1. The map exhibited three domains. (1) A domain of dynamic recovery occurs in the temperature range 800-degrees-C to 1075-degrees-C and strain rate range 0.02 to 2 s-1, with a peak efficiency of 18 pct occurring at 950-degrees-C and 0.1 s-1. Transmission electron microscope (TEM) micrographs revealed stable subgrain structure in this domain with the subgrain size increasing exponentially with an increase in temperature. (2) A domain exhibiting grain boundary cracking occurs at temperatures lower than 800-degrees-C and strain rates lower than 0.01 s-1. (3) A domain exhibiting intense grain boundary cavitation occurs at temperatures higher than 1075-degrees-C. The material did not exhibit a dynamic recrystallization (DRX) domain, unlike other superalloys. At strain rates higher than about 1 s-1, the material exhibits flow instabilities manifesting as kinking of the elongated grains and adiabatic shear bands. The material may be safely worked in the domain of dynamic recovery but can only be statically recrystallized.

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Microstructural control in hot working of IN-718 superalloy using processing map

The hot-working characteristics of IN-718 are studied in the temperature range 900 degrees C to 1200 degrees C and strain rate range 0.001 to 100 s(-1) using hot compression tests. Processing maps for hot working are developed on the basis of the strain-rate sensitivity variations with temperature and strain rate and interpreted using a dynamic materials model. The map exhibits two domains of dynamic recrystallization (DRX): one occurring at 950 degrees C and 0.001 s(-1) with an efficiency of power dissipation of 37 pct and the other at 1200 degrees C and 0.1 s(-1) with an efficiency of 40 pct. Dynamic recrystallization in the former domain is nucleated by the delta(Ni3Nb) precipitates and results in fine-grained microstructure. In the high-temperature DRX domain, carbides dissolve in the matrix and make interstitial carbon atoms available for increasing the rate of dislocation generation for DRX nucleation. It is recommended that IN-718 may be hot-forged initially at 1200 degrees C and 0.1 s(-1) and finish-forged at 950 degrees C and 0.001 s(-1) so that fine-grained structure may be achieved. The available forging practice validates these results from processing maps. At temperatures lower than 1000 degrees C and strain rates higher than 1 s(-1), the material exhibits adiabatic shear bands. Also, at temperatures higher than 1150 degrees C and strain rates more than 1 s(-1), IN-718 exhibits intercrystalline cracking. Both these regimes may be avoided in hot-working IN-718.

Modified crack closure integral (MCCI) for 3-d problems using 20 noded brick elememnts

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Combined convection in power-law fluids along a nonisothermal vertical plate in a porous medium

The problem of combined convection from vertical surfaces in a porous medium saturated with a power-law type non-Newtonian fluid is investigated. The transformed conservation laws are solved numerically for the case of variable surface heat flux conditions. Results for the details of the velocity and temperature fields as well as the Nusselt number have been presented. The viscosity index ranged from 0.5 to 2.0.

Dynamic recrystallisation during hot working of Zr-2 center dot 5Nb: Characterisation using processing maps

The characteristics of the hot deformation of Zr-2.5Nb (wt-%) in the temperature range 650-950 degrees C and in the strain rate range 0.001-100 s(-1) have been studied using hot compression testing. Two different preform microstructures: equiaxed (alpha + beta) and beta transformed have been investigated. For this study, the approach of processing maps has been adopted and their interpretation carried out using the dynamic materials model. The efficiency of power dissipation given by [2m/(m + 1)], where m is the strain rate sensitivity, is plotted as a function of temperature and strain rate to obtain a processing map. A domain of dynamic recrystallisation has been identified in the maps of equiaxed (alpha + beta) and beta transformed preforms. In the case of equiaxed (alpha + beta), the stress-strain curves are steady state and the dynamic recrystallisation domain in the map occurs with a peak efficiency of 45% at 850 degrees C and 0.001 s(-1). On the other hand the beta transformed preform exhibits stress-strain curves with continuous flow softening. The corresponding processing map shows a domain of dynamic recrystallisation occurring by the shearing of alpha platelets followed by globularisation with a peak efficiency of 54% at 750 degrees C and 0.001 s(-1). The characteristics of dynamic recrystallisation are analysed on the basis of a simple model which considers the rates of nucleation and growth of recrystallised gains. Calculations show that these two rates are nearly equal and that the nucleation of dynamic recrystallisation is essentially controlled by mechanical recovery involving the cross-slip of screw dislocations. Analysis of flow instabilities using a continuum criterion revealed that Zi-2.5Nb exhibits flow localisation at temperatures lower than 700 degrees C and strain rates higher than 1 s(-1).

Electron donor-acceptor complexes of I-2 with diethyl ether and diethyl sulphide. An ab initio MO study

The charge-transfer complexes of I-2 with the n-donors diethyl ether and diethyl sulfide were studied at the Hartree-Fock and MP2 levels. The structures were fully optimized using the 3-21G((*)) basis set as well as with effective core potentials. The calculations consistently yield a C-2v structure for the ether-I-2 complex, but an unsymmetrical form for the sulfide-I-2 complex. A natural bond orbital analysis and the BSSE-corrected complexation energies reveal stronger interactions in the sulfide complex. The computed orbital energies of the monomers and complexes reproduce the trends in experimentally observed vertical ionization potentials.