The Blackett Memorial Lecture, 1991: Chemical Insights into High-Temperature Superconductors

The high-temperature superconductors are complex oxides, generally containing two-dimensional CuO2 sheets. Various families of the cuprate superconductors are described, paying special attention to aspects related to oxygen stoichiometry, phase stability, synthesis and chemical manipulation of charge carriers. Other aspects discussed are chemical applications of cuprates, possibly as gas sensors and copper-free oxide superconductors. All but the substituted Nd and Pr cuprates are hole-superconductors. Several families of cuprates show a nearly constant n(h) at maximum T(c). Besides this universality, the cuprates exhibit a number of striking common features. Based on Cu(2p) photoemission studies, it is found that the Cu-O charge-transfer energy, DELTA, and the Cu(3d)-O(2p) hybridization strength, t(pd), are key factors in the superconductivity of cuprates. The relative intensity of the satellite in the Cu(2p) core-level spectra, the polarizability of the CuO2 sheets as well as the hole concentration are related to DELTA/t(pd). These chemical bonding factors have to be explicitly taken into account in any model for superconductivity of the cuprates.

Differential stability of beta-sheets and alpha-helices in beta-lactamase: a high temperature molecular dynamics study of unfolding intermediates

Beta-Lactamase, which catalyzes beta-lactam antibiotics, is prototypical of large alpha/beta proteins with a scaffolding formed by strong noncovalent interactions. Experimentally, the enzyme is well characterized, and intermediates that are slightly less compact and having nearly the same content of secondary structure have been identified in the folding pathway. In the present study, high temperature molecular dynamics simulations have been carried out on the native enzyme in solution. Analysis of these results in terms of root mean square fluctuations in cartesian and [phi, psi] space, backbone dihedral angles and secondary structural hydrogen bonds forms the basis for an investigation of the topology of partially unfolded states of beta-lactamase. A differential stability has been observed for alpha-helices and beta-sheets upon thermal denaturation to putative unfolding intermediates. These observations contribute to an understanding of the folding/unfolding processes of beta-lactamases in particular, and other alpha/beta proteins in general.

High-temperature low-cycle fatigue behavior of a NIMONIC PE-16 superalloy—Correlation with deformation and fracture

Low-cycle fatigue (LCF) responses of NIMONIC PE-16 for various prior microstructures and strain amplitudes have been evaluated and the fatigue behavior has been explained in terms of the operative deformation mechanisms. Total strain-controlled LCF tests were performed at 923 K on samples possessing three different prior microstructures: alloy A in solution-annealed condition (free of γ′ and carbides), alloy B with double aging treatment (spherical γ′ of 18-nm diameter and M23C6), and alloy C with another double aging treatment (γ′ of size 35 nm, MC and M23C6). All three microstructures exhibited an intial cyclic hardening followed by a period of gradual softening at 923 K. Coffin-Manson plots describing the plastic strain amplitudevs number of reversals to failure showed that alloy A had maximum fatigue life while C showed the least. Alloy B exhibited a two-slope behavior in the Coffin-Manson plot over the strain amplitudes investigated. This has been ascribed to the change in the degree of homogeneity of deformation at high and low strain amplitudes. Transmission electron microscopic studies were carried out to characterize the various deformation mechanisms and precipitation reactions occurring during fatigue testign. Fresh precipitation of fine γ′ was confirmed by the development of “mottled contrast” in alloy C. Evidence for the shearing of the ordered γ′ precipitates was revealed by the presence of superdislocations in alloy C. Repeated shearing during cyclic loading led to the reduction in the size of the γ′ and consequent softening. Coarser γ′ precipitates were associated with Orowan loops. The observed fatigue behavior has been rationalized based on the micromechanisms stated above and on the degree of homogenization of slip assessed by slipband spacing measurements on tested samples.

Influence of grain size on high temperature fracture in a Mg AZ31 alloy

Tensile experiments at 673 K and grain sizes from similar to 8 to 17 mu m revealed large ductility at a low strain rate and a reduced ductility at a high strain rate, corresponding to a change from a high to a low value for the strain rate sensitivity. High strain rate deformation led to fracture by flow localization, whereas low strain rate deformation involved fracture by cavity nucleation and growth. Analysis revealed that grain boundary migration can assist significantly in reducing the stress concentrations caused by grain boundary sliding, thereby retarding cavity nucleation. Calculations demonstrate that the interlinkage of voids parallel and perpendicular to the tensile axis occurs significantly, so that it is not always possible to use the cavity shapes to distinguish between diffusion and plasticity controlled growth. Cavitation damage evolves slowly in materials with a coarser grain size because of reduced nucleation related to a reduction in the strain rate sensitivity and associated grain boundary sliding. (C) 2011 Elsevier B.V. All rights reserved.

Effect of strain rate on the high-temperature low-cycle fatigue properties of a nimonic PE-16 superalloy

Strain-rate effects on the low-cycle fatigue (LCF) behavior of a NIMONIC PE-16 superalloy have been evaluated in the temperature range of 523 to 923 K. Total-strain-controlled fatigue tests were per-formed at a strain amplitude of +/-0.6 pct on samples possessing two different prior microstructures: microstructure A, in the solution-annealed condition (free of gamma' and carbides); and microstructure B, in a double-aged condition with gamma' of 18-nm diameter and M23C6 carbides. The cyclic stress response behavior of the alloy was found to depend on the prior microstructure, testing temperature, and strain rate. A softening regime was found to be associated with shearing of ordered gamma' that were either formed during testing or present in the prior microstructure. Various manifestations of dynamic strain aging (DSA) included negative strain rate-stress response, serrations on the stress-strain hysteresis loops, and increased work-hardening rate. The calculated activation energy matched well with that for self-diffusion of Al and Ti in the matrix. Fatigue life increased with an increase in strain rate from 3 x 10(-5) to 3 x 10(-3) s-1, but decreased with further increases in strain rate. At 723 and 823 K and low strain rates, DSA influenced the deformation and fracture behavior of the alloy. Dynamic strain aging increased the strain localization in planar slip bands, and impingement of these bands caused internal grain-boundary cracks and reduced fatigue life. However, at 923 K and low strain rates, fatigue crack initiation and propagation were accelerated by high-temperature oxidation, and the reduced fatigue life was attributed to oxidation-fatigue interaction. Fatigue life was maximum at the intermediate strain rates, where strain localization was lower. Strain localization as a function of strain rate and temperature was quantified by optical and scanning electron microscopy and correlated with fatigue life.

High-temperature reactions of alkali and plagioclase feldspars with alkali and alkaline-earth chlorides-formation of celsian

High-temperature reactions (Ca 900-degrees-C) involving albite, K-feldspar or plagioclase and K, Ba-or K, Sr chlorides were experimentally studied. These experiments reveal that the reaction between K-exchanged albite, potash feldspar, or plagioclase and Ba-chloride/Ba-K chloride results in the formation of celsian by the breakdown of the starting feldspar structure above 800-degrees-C. Sr-feldspar does not form under similar conditions. A size-effect of the large M-site cation appears to be responsible for the formation of celsian. The reaction between K-feldspar and barium chloride may be used as a method for synthesizing celsian.

High-temperature stability of Ca2ZrSi4O12

The standard Gibbs free energy of formation of orthorhombic Ca2ZrSi4O12 from component oxides ZrO2 (monoclinic), CaO (rock salt), and SiO2 (quartz) has been determined in the temperature range 973 to 1273 K using a solid-state cell incorporating single-crystal CaF2 as the electrolyte: Delta G(f) degrees = -219930 + 11.77T (+/- 1500) J.mol(-1) This is the only quantitative information now available on the stability of Ca2ZrSi4O12.

Radiation induced modifications on microstructure and related properties of high temperature superconductor YBCO

Role of swift heavy ion irradiation on the modification of transport and structural properties of high temperature superconductors is studied. Good quality YBCO thin films prepared by high pressure oxygen sputtering and laser ablation were used in this investigation. Resistivity and atomic force microscopy (AFM) were mainly used to probe superconducting and microstructural modifications resulted from the irradiation of high energy and heavy ions like 100 MeV oxygen and 200 MeV silver. Radiation induced sputtering or erosion is likely to be a major disastrous component of such high energy irradiation that could be powerful in masking phase coherence effects, atleast in grain boundaries. The extent of damage/nature of defects other than columnar defects produced by swift heavy ions is discussed in the light of AFM measurements. The effect of high energy oxygen ion irradiation is anomalous. A clear annealing effect at higher doses is seen. (C) 1999 Elsevier Science B.V. All rights reserved.

High temperature phase chemistry of system Eu-Pd-O

An isothermal section of the phase diagram for the system Eu - Pd - O at 1223 K has been established by equilibration of samples representing 20 different compositions, and phase identification after quenching by optical and scanning electron microscopy, X-ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides, Eu4PdO7, Eu2PdO4, and Eu2Pd2O5, were identified. Liquid alloys and the intermetallic compounds EuPd2 and EuPd3 were found to be in equilibrium with EuO. The compound EuPd3 was also found to coexist separately with Eu3O4 and Eu2O3. The oxide phase in equilibrium with EuPd5 and Pd rich solid solution was Eu2O3. Based on the phase relations, four solid state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 925 to 1350 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to crosscheck the data. An advanced version of the solid state cell incorporating a buffer electrode with yttria stabilised zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high temperature thermodynamic measurements. Equations for the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides Eu2O3 with C type structure and PdO have been established. Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Eu - Pd - O have been developed.

Effect of spinel second phase on high temperature deformation in alumina

Constant stress compression creep experiments were carried out on high purity alumina composites with spinel contents of 8 and 30%, corresponding to a situation with isolated and interconnected second phases. The creep experiments were conducted over a stress and temperature range of 10 to 150 MPa and 1623 to 1723 K, respectively. Analysis of the experimental data indicated that the variation in spinel content did not have any influence on high temperature deformation in the composite. The spinel phase retards grain growth, and this may enhance superplasticity in alumina-spinel composites.

High-temperature deformation processing maps for a NiTiCu shape memory alloy

The properties of widely used Ni-Ti-based shape memory alloys (SMAs) are highly sensitive to the underlying microstructure. Hence, controlling the evolution of microstructure during high-temperature deformation becomes important. In this article, the ``processing maps'' approach is utilized to identify the combination of temperature and strain rate for thermomechanical processing of a Ni(42)Ti(50)Cu(8) SMA. Uniaxial compression experiments were conducted in the temperature range of 800-1050 degrees C and at strain rate range of 10(-3) and 10(2) s(-1). Two-dimensional power dissipation efficiency and instability maps have been generated and various deformation mechanisms, which operate in different temperature and strain rate regimes, were identified with the aid of the maps and complementary microstructural analysis of the deformed specimens. Results show that the safe window for industrial processing of this alloy is in the range of 800-850 degrees C and at 0.1 s(-1), which leads to grain refinement and strain-free grains. Regions of the instability were identified, which result in strained microstructure, which in turn can affect the performance of the SMA.