On the microstructure-tensile property correlations in bulk metallic glass matrix composites with crystalline dendrites

Bulk metallic glass (BMG) matrix composites with crystalline dendrites as reinforcements exhibit a wide variance in their microstructures (and thus mechanical properties), which in turn can be attributed to the processing route employed, which affects the size and distribution of the dendrites. A critical investigation on the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify ``structure-property'' connections in these materials. This was accomplished by employing four different processing methods-arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat-on composites with two different dendrite volume fractions, V-d. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, lambda, and dendrite size, delta, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite's properties are insensitive to the microstructural length scales when V-d is high (similar to 75%), whereas they become process dependent for relatively lower V-d (similar to 55%). Larger delta in arc-melted and forged specimens result in higher ductility (7-9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer lambda result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Indentation size effect and shear transformation zone size in a bulk metallic glass in two different structural states

The existence of an indentation size effect (ISE) in the onset of yield in a Zr-based bulk metallic glass (BMG) is investigated by employing spherical-tip nanoindentation experiments. Statistically significant data on the load at which the first pop-in in the displacement occurs were obtained for three different tip radii and in two different structural states (as-cast and structurally relaxed) of the BMG. Hertzian contact mechanics were employed to convert the pop-in loads to the maximum shear stress underneath the indenter. Results establish the existence of an ISE in the BMG of both structural states, with shear yield stress increasing with decreasing tip radius. Structural relaxation was found to increase the yield stress and decrease the variability in the data, indicating ``structural homogenization'' with annealing. Statistical analysis of the data was employed to estimate the shear transformation zone (STZ) size. Results of this analysis indicate an STZ size of similar to 25 atoms, which increases to similar to 34 atoms upon annealing. These observations are discussed in terms of internal structure changes that occur during structural relaxation and their interaction with the stressed volumes in spherical indentation of a metallic glass. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Influence of nature of support on the catalytic activity of supported molybdenum-oxo species in benzyl alcohol conversion

Supported catalysts containing 15 wt.% of molybdenum have been prepared by the incipient wetness impregnation method. CaO, MgO, Al2O3, Zr(OH)4 and Al(OH)3 have been used as supports for the preparation of supported Mo catalysts. Characterisation of all the materials prepared has been carried out through BET surface area measurement, X-ray diffractometry and FT-IR spectroscopy. Catalytic activity measurements have been carried out with reference to structure-sensitive benzyl alcohol conversion in the liquid phase. The percentage conversion of benzyl alcohol to benzaldehyde and toluene varied over a large range depending on the support used for the preparation of catalysts, indicating the importance of the support on catalytic activity of Mo catalysts. Al(OH)3 has been found to be the best support for molybdenum among all the supports used. Support–metal interaction (SMI) has been found to play an important role in determining the catalytic activity of supported catalysts.

On the mechanism and the length scales involved in the ductile fracture of a bulk metallic glass

Some bulk metallic glasses (BMGs) exhibit high crack initiation toughness due to shear band mediated plastic flow at the crack tip and yet do not display additional resistance to crack growth due to the lack of a microstructure. Thus, at crack initiation, the fracture behavior of BMGs transits from that of ductile alloys to that of brittle ceramics. In this paper, we attempt to understand the physics behind the characteristic length from the notch root at which this transition occurs, through testing of four-point bend specimens made of a nominally ductile Zr-based BMG in three different structural states. In the as-cast state, both symmetric (mode I) and asymmetric (mixed mode) bend specimens are tested. The process of shear band mediated plastic flow followed by crack initiation at the notch root was monitored through in situ imaging. Results show that stable crack growth occurs inside a dominant shear band through a distance of, similar to 60 mu m, irrespective of the structural state and mode mixity, before attaining criticality. Detailed finite element simulations show that this length corresponds to the distance from the notch root over which a positive hydrostatic stress gradient prevails. The mean ridge heights on fractured surfaces are found to correlate with the toughness of the BMG. The Argon and Salama model, which is based on the meniscus instability phenomenon at the notch root, is modified to explain the experimentally observed physics of fracture in ductile BMGs. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effects of different modes of hot cross-rolling in 7010 aluminum alloy: part I. evolution of microstructure and texture

The current study describes the evolution of microstructure and texture in an Al-Zn-Mg-Cu-Zr-based 7010 aluminum alloy during different modes of hot cross-rolling. Processing of materials involves three different types of cross-rolling. The development of texture in the one-step cross-rolled specimen can be described by a typical beta-fiber having the maximum intensity near Copper (Cu) component. However, for the multi-step cross-rolled specimens, the as-rolled texture is mainly characterized by a strong rotated-Brass (Bs) component and a very weak rotated-cube component. Subsequent heat treatment leads to sharpening of the major texture component (i.e., rotated-Bs). Furthermore, the main texture components in all the specimens appear to be significantly rotated in a complex manner away from their ideal positions because of non-symmetric deformations in the two rolling directions. Detailed microstructural study indicates that dynamic recovery is the dominant restoration mechanism operating during the hot rolling. During subsequent heat treatment, static recovery dominates, while a combination of particle-stimulated nucleation (PSN) and strain-induced grain boundary migration (SIBM) causes partial recrystallization of the grain structure. The aforementioned restoration mechanisms play an important role in the development of texture components. The textural development in the current study could be attributed to the combined effects of (a) cross-rolling and inter-pass annealing that reduce the intensity of Cu component after each successive pass, (b) recrystallization resistance of Bs-oriented grains, (c) stability of Bs texture under cross-rolling, and (d) Zener pinning by Al3Zr dispersoids.

Growth of hafnium and zirconium suicides by reactive diffusion

Diffusion controlled growth of the phases in Hf-Si and Zr-Si systems are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane, detected based on the grain morphology, indicates that disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 +/- 37 and 346 +/- 34 kJ mol(-1), respectively. The same is calculated for the HfSi phase as 485 +/- 42 kJ mol(-1). The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 +/- 36 and 348 +/- 34 kJ mol(-1), respectively. (C) 2013 Elsevier B.V. All rights reserved.

Growth of hafnium and zirconium suicides by reactive diffusion

Diffusion controlled growth of the phases in Hf-Si and Zr-Si systems are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane, detected based on the grain morphology, indicates that disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 +/- 37 and 346 +/- 34 kJ mol(-1), respectively. The same is calculated for the HfSi phase as 485 +/- 42 kJ mol(-1). The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 +/- 36 and 348 +/- 34 kJ mol(-1), respectively. (C) 2013 Elsevier B.V. All rights reserved.

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La3+ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

Neoarchean continental growth through arc magmatism in the Nilgiri Block, southern India

The formation and growth of continental crust in the Archean have been evaluated through models of subduction-accretion and mantle plume. The Nilgiri Block in southern India exposes exhumed Neoarchean lower crust, uplifted to heights of 2500 m above sea level along the north western margin of the Peninsula. Major lithologies in this block include charnockite with or without garnet, anorthosite-gabbro suite, pyroxenite, amphibolite and hornblende-biotite gneiss (TTG). All these rock types are closely associated as an arc magmatic suite, with diffuse boundaries and coeval nature. The charnockite and hornblende-biotite gneisses (TTG) show SiO2 content varying from 64 to 73 wt.%. The hornblende-biotite gneisses (TTG) are high-Al type with Al2O3 >15 wt.% whereas the charnockites show Al2O3 <15 wt.%. The composition of charnockite is mainly magnesian and calcic to calc-alkaline. The mafic-ultramafic rocks show composition close to that of tholeiitic series. The low values of K(2)o (<3 wt.%), (K/Rb)/K2O (<500), Zr/Ti, and trace element ratios like (La/Yb)n/(Sr/Y), (Y/Nb), (Y + Nb)/Rb, (Y+Ta)/Rb, Yb/Ta indicate a volcanic arc signature for these rocks. The geochemical signature is consistent with arc magmatic rocks generated through oceanic plate subduction. The primitive mantle normalized trace element patterns of these rocks display enrichment in large ion lithophile elements (LILE) and comparable high field strength elements (HFSE) in charnockite and hornblende-biotite gneisses (TTG) consistent with subduction-related origin. Primitive mantle normalized REE pattern displays an enrichment in LREE in the chamockite and hornblende-biotite gneisses (TTG) as compared to a flat pattern for the mafic rocks. The chondrite normalized REE patterns of zircons of all the rock types reveal cores with high HREE formed at ca. 2700 Ma and rims with low HREE formed at 2500-2450 Ma. Log-transformed La/Th-Nb/Th-Sm/Th-Yb/Th discrimination diagram for the mafic and ultramafic rocks from Nilgiri displays a transition from mid-oceanic ridge basalt (MORB) to island arc basalt (IAB) suggesting a MORB source. The U-Pb zircon data from the charnockites, mafic granulites and hornblende-biotite gneisses (TTG) presented in our study show that the magma generation during subduction and accretion events in this block occurred at 2700-2500 Ma. Together with the recent report on Neoarchean supra-subduction zone ophiolite suite at its southern margin, the Nilgiri Block provides one of the best examples for continental growth through vertical stacking and lateral accretion in a subduction environment during the Neoarchean. (c) 2014 Elsevier B.V. All rights reserved.

Effect of hydrogen on the yielding behavior and shear transformation zone volume in metallic glass ribbons

The effect of hydrogen (H) charging on the shear yield strength (tau(max)) and shear transformation zone volume (Omega) of Ni-Nb-Zr metallic glass ribbons, with varying Zr content, were studied through the first pop-in loads during nanoindentation. Weight gain measurements after H charging and desorption studies were utilized to identify how the total H absorbed during charging is partitioned into mobile and immobile (or trapped) parts. These, in turn, indicate the significant role of H mobility in the amorphous structure on the yielding behavior. In high-Zr alloys, tau(max) increases significantly whereas Omega decreases. In low-Zr alloys, a slight decrease in tau(max) and increase in Omega were noted. These experimental observations are rationalized in terms of the mobility of the absorbed H in the amorphous structure and the possible role of it in the shear transformation zone dynamics during deformation of the metallic glass. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of Zirconium on the Densification of Reactively Hot-Pressed Zirconium Carbide

Densification mechanisms involved during reactive hot pressing (RHP) of zirconium carbide (ZrC) have been studied. RHP has been carried out using zirconium (Zr) and graphite (C) powders in the molar ratios 1:0.5, 1:0.67, 1:0.8, and 1:1 at 40MPa, 800 degrees C-1200 degrees C for different durations. The volume fractions of phases formed, including porosity, are determined from the measured density and from Rietveld analysis. Increased densification with an increasing nonstoichiometry in carbon has been observed. Microstructural and X-ray diffraction observations coupled with the predictions of a model based on the constitutive laws governing plastic flow of zirconium suggest that the better densification of nonstoichiometric compositions arise from the higher amount of starting Zr and also the longer duration of its availability for plastic flow during RHP. Volume shrinkage due to reaction between Zr and C and the gradual elimination of the soft metal phase limit the final density achievable. Based on these observations, a two-step RHP carried out at 800 degrees C and 1200 degrees C leads to a better densification than a single RHP at 1200 degrees C.

Structural and magnetic properties of ultra-small scale eutectic CoFeZr alloys

Aiming to develop high mechanical strength and toughness by tuning ultrafine lamellar spacing of magnetic eutectic alloys, we report the mechanical and magnetic properties of the binary eutectic alloys Co90.5Zr9.5 and Fe90.2Zr9.8, as well as the pseudo-binary eutectic alloys Co82.4Fe8Zr9.6, Co78Fe12.4Zr9.6 and Co49.2Fe49.2Zr9.6 developed by suction-casting. The lower lamellar spacing around 100 nm of the eutectics Co49.2Fe49.2Zr9.6 yields a high hardness of 713(+/- 20) VHN. Magnetic measurements reveal high magnetic moment of 1.92 mu B (at 5 K) and 1.82 mu B (at 300 K) per formula unit for this composition. The magnetization vs. applied field data at 5 K show a directional preference to some extent and therefore smaller non-collinear magnetization behavior compared to Co11Zr2 reported in the literature due to exchange frustration and transverse spin freezing owing to the presence of smaller Zr content. The decay of magnetization as a function of temperature along the easy axis of magnetization of all the eutectic compositions can be described fairly well by the spin wave excitation equation Delta M/M(0) = BT3/2 + CT5/2. (C) 2014 Elsevier B.V. All rights reserved.

Strain-induced electronic phase transition and strong enhancement of thermopower of TiS2

Using first-principles density functional theory calculations, we show a semimetal to semiconducting electronic phase transition for bulk TiS2 by applying uniform biaxial tensile strain. This electronic phase transition is triggered by charge transfer from Ti to S, which eventually reduces the overlap between Ti-(d) and S-(p) orbitals. The electronic transport calculations show a large anisotropy in electrical conductivity and thermopower, which is due to the difference in the effective masses along the in-plane and out-of-plane directions. Strain-induced opening of band gap together with changes in dispersion of bands lead to threefold enhancement in thermopower for both p-and n-type TiS2. We further demonstrate that the uniform tensile strain, which enhances the thermoelectric performance, can be achieved by doping TiS2 with larger iso-electronic elements such as Zr or Hf at Ti sites.

Precipitation response of the magnesium alloy WE43 in strained and unstrained conditions

The precipitation behavior of the magnesium alloy WE43 (Mg-4%Y-2.3%Nd-0.5%Zr) has been studied in strained and unstrained conditions using Transmission Electron Microscopy (TEM). Ageing treatments were carried out at three temperatures, namely 210 degrees C, 230 degrees C and 260 degrees C. The precipitation sequence during static aging of solution treated (ST) samples has been identified as ST —> beta'' —> beta' followed by the formation of beta(1) and equilibrium beta precipitates form after very long ageing periods. Dynamic precipitation was observed during high temperature deformation, leading to the formation of beta' and intermediate beta(1) precipitates. The strained samples, when further heat treated, resulted in the transformation of beta(1) into beta equilibrium precipitates. The sequence of dynamic precipitation is ST —> beta(1) —> beta and ST —> beta'. (C) 2014 Elsevier B.V. All rights reserved.

On the strain rate sensitivity of plastic flow in metallic glasses

The nanoindentation technique was employed to examine the strain rate sensitivity, m, and its dependence on the structural state of a Zr-based bulk metallic glass (BMG). The free volume content in the BMG was varied by examining samples in the as-cast (AC), shot-peened (SP), and structurally relaxed (SR) states. Hardness values measured at different loading rates and over a temperature range of 300-423 K as well as the strain-rate jump tests conducted in the quasi-static regime at room temperature, show that m is always negative. All the load-displacement (P-h) curves in this temperature regime exhibit serrated load-displacement responses, indicating that the shear band mediated inhomogeneous plastic flow governs deformation. Such localization of flow and associated softening is the raison d'etre for the negative m. Significant levels of pile-up around the indents were also noted. The order in the average values of hardness, pile-up heights, and the displacement bursts on the P-h curves was always such that SR > AC > SP, which is also the order of increasing free volume content. These observations were utilized to discuss the reasons for the negative strain rate sensitivity, and its dependence on the structural state of metallic glasses. It is suggested that the positive values of m reported in the literature for them are possibly experimental artefacts that arise due to large pile ups around the indents which lead to erroneous estimation in hardness values. (C) 2014 Elsevier B.V. All rights reserved.