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.

Fracture in metallic glasses: mechanics and mechanisms

Significant progress in understanding the mechanical behavior of metallic glasses (MGs) was made over the past decade, particularly on mechanisms of plastic deformation. However, recent research thrust has been on exploring the mechanics and physics of fracture. MGs can be very brittle with K-Ic values similar to silicate glasses and ceramics or very tough with K-Ic akin to high toughness crystalline metals. Even the tough MGs can become brittle with structural relaxation following annealing at temperatures close to glass transition temperature (T-g). Detailed experimental studies coupled with complementary numerical simulations of the recent past have provided insights on the micromechanisms of failure as well as nature of crack tip fields, and established the governing fracture criteria for ductile and brittle glasses. In this paper, the above advances are reviewed and outstanding issues in the context of fracture of amorphous alloys that need to be resolved are identified.

On the variability in fracture toughness of `ductile' bulk metallic glasses

The mode I fracture toughness, K-Ic, of ductile bulk metallic glasses (BMGs) exhibits a high degree of specimen-to-specimen variability. By conducting fracture experiments in modes I and II, we demonstrate that the observed high variability in mode I, vis-a-vis mode II, is a result of highly variable propensity for the conversion of shear bands into cracks in mode I whereas in mode II, crack growth direction is fixed. Thus, the measured variability in K-Ic is intrinsic to the nature of BMGs. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Variation of Electrical Resistivity with High Pressure in Ge-Te-Sn Glasses: A Composition Dependent Study

The variation of normalized electrical resistivity in the system of glasses Ge15Te85-xSnx with (1 <= x <= 5) has been studied as a function of high pressure for pressures up to 9.5 GPa. It is found that with the increase in pressure, the resistivity decreases initially and shows an abrupt fall at a particular pressure, indicating the phase transition from semiconductor to near metallic at these pressures, which lie in the range 1.5-2.5 GPa, and then continues being metallic up to 9.5 GPa. This transition pressure is seen to decrease with the increase in the percentage content of tin due to increasing metallicity of tin. The semiconductor to near metallic transition is exactly reversible and may have its origin in a reduction of the band gap due to high pressure.

Thermal and spectroscopic investigations of glasses in the system PbO-PbCl2-PbBr2

Glass formation has been examined in the system 15PbO.xPbCl(2).(85-x)PbBr2 (where 0 <= x <= 25)where the PbO concentration is kept constant while PbCl2 and PbBr2 concentrations are varied. The glasses have been examined using thermal and spectroscopic techniques. T-8, Delta C-p, refractive index, optical basicity have been found to remain unaffected by the composition which is a curious feature of these glasses. It is found that there is a wide infrared window available for use in the investigated glasses. The IR window extends from 1000 to 1500 cm(-1) and in glasses where PbCl2 is less than 20 mol%, the window extends up to 2260 cm(-1). X-ray photoelectron spectra (XPS) revealed that the 4f(5/2) and 4f(7/2) peaks due to f-level transitions have a constant difference in energies, but with energy and FWHM values that varying sensitively and systematically with composition. The observations are discussed and suitable explanations are provided.

Conductivity studies on microwave synthesized glasses

Conductivity measurements have been made on x V O-2(5) - (100-x) 0.5 Na2O + 0.5 B2O3] (where 10 a parts per thousand currency sign x a parts per thousand currency sign 50) glasses prepared by using microwave method. DC conductivity (sigma) measurements exhibit temperature-and compositional-dependent trends. It has been found that conductivity in these glasses changes from the predominantly `ionic' to predominantly `electronic' depending upon the chemical composition. The dc conductivity passes through a deep minimum, which is attributed to network disruption. Also, this nonlinear variation in sigma (dc) and activation energy can be interpreted using ion-polaron correlation effect. Electron paramagnetic resonance (EPR) and impedance spectroscopic techniques have been used to elucidate the nature of conduction mechanism. The EPR spectra reveals, in least modified (25 Na2O mol%) glasses, conduction is due to the transfer of electrons via aliovalent vanadium sites, while in highly modified (45 Na2O mol%) glasses Na+ ion transport dominates the electrical conduction. For highly modified glasses, frequency-dependent conductivity has been analysed using electrical modulus formalism and the observations have been discussed.

Impedance spectroscopic studies on microwave synthesized NaPO3-V2O5 glasses containing SO42- ions

Impedance spectroscopic studies on modified phospho-vanadate glasses containing SO42- ions have been carried out over wide range of frequency. Modulated DSC studies suggest that the addition of alkali salt makes the glass less rigid and more fragile. The frequency dependent impedance data has been used to calculate d.c conductivity and activation energies. These values are comparable with the other ionic liquids. The conductivity and relaxation phenomenon was rationalized using universal a.c conductivity power law and modulus formalism. The activation energies for relaxation mechanism was also determined using imaginary parts of electrical modulus peaks which were close to those of the d.c conductivity implying the involvement of similar energy barriers in both the processes. Kohlrausch-William-Watts (KWW) stretched exponent beta, is temperature insensitive and power law (s) exponent is temperature dependent. The enhanced conductivity in these glasses is attributed to the depolymerised structure in which migration of Na+ ions proceeds in an expanded network comprising SO42- ions in the interstitials. The effect of structure on activation energy is well supported by abinitio DFT computations. (C) 2015 Elsevier B.V. All rights reserved.

Dependence of shear yield strain and shear transformation zone on the glass transition temperature in thin film metallic glasses

The dependence of shear yield strain, the activation energy and volume of shear transformation zone on the glass transition temperature was investigated through the analysis of statistical distributions of the first pop-in events during spherical indentation of four different thin film metallic glasses. Only the Cu-Zr metallic glass exhibits a bimodal distribution of the first pop-in loads, whereas W-Ru-B, Zr-Cu-Ni-Al and La-Co-Al metallic glasses show an unimodal distribution. Results show that shear yield strain and activation energy of shear transformation zone decrease whereas the volume of shear transformation zone increases with increasing homologous temperature, indicating that it is the activation energy rather than the volume of shear transformation zone that controls shear yield strain. (C) 2015 Elsevier B.V. All rights reserved.

Effect Of High Pressure On The Electrical Resistivity Of Ge-Te In Glasses

The variation in the electrical resistivity of the chalcogenide glasses Ge15Te85-x has been studied as a function of high pressure for pressures up to 8.5GPa. All the samples studied undergo a semi-conductor to metallic transition in a continuous manner at pressures between 1.5-2.5GPa. The transition pressure at which the samples turn metallic increases with increase in percentage of Indium. This increase is a direct consequence of the increase in network rigidity with the addition of Indium. At a constant pressure of 0.5GPa, the normalized resistivity shows some signature of the existence of the intermediate phase. Samples recovered after a pressure cycle remain amorphous suggesting that the semi-conductor to metallic transition arises from a reduction of the band gap due to pressure or the movement of the Fermi level into the conduction or valence band.

On the critical thickness for non-localized to localized plastic flow transition in metallic glasses: A molecular dynamics study

Molecular dynamics simulations were employed to investigate the specimen thickness-dependent tensile behavior of a series of Cu(x)Z(100-x) (x = 20, 40, 50, 64 and 80 at%) metallic glass (MG) films, with a particular focus on the critical thickness, tc, below which non-localized plastic flow takes place. The simulation results reveal that while the transition occurs in all the alloys examined, t(c) is sensitive to the composition. We rationalize t(c) by postulating that the strain energy stored in the sample at the onset of plastic deformation has to be sufficient for the formation of shear bands. The composition-dependence of t(c) was found to correlate with the average activation energy of the atomic level plastic deformation events. (C) 2015 Elsevier Ltd. All rights reserved.

Electrical conductivity and dielectric relaxation studies on microwave synthesized Na2SO4 center dot NaPO3 center dot MoO3 glasses

Electrical conductivity and dielectric relaxation studies on SO4 (2-) doped modified molybdo-phosphate glasses have been carried out over a wide range of composition, temperature and frequency. The d.c. conductivities which have been measured by both digital electrometer (four-probe method) and impedance analyser are comparable. The relaxation phenomenon has been rationalized using electrical modulus formalism. The use of modulus representation in dielectric relaxation studies has inherent advantages viz., experimental errors arising from the contributions of electrode-electrolyte interface capacitances are minimized. The relaxation observed in the present study is non-Debye type. The activation energies for relaxation were determined using imaginary parts of electrical modulus peaks which were close to those of the d.c. conductivity implying the involvement of similar energy barriers in both the processes. The enhanced conductivity in these glasses can be attributed to the migration of Na+, in expanded structures due to the introduction of SO4 (2-) ions.

A.c. conductivity studies on the silver molybdo-arsenate glassy system

A new quaternary fast-ion conducting silver molybdo-arsenate [Agl-Ag2O-(MoO3 + As2O5)] (SMA) glassy system has been prepared using the melt-quenching technique for various dopant salt (Agl) concentrations by fixing the formers (MoO3 + As2O5) composition and the modifier (Ag2O) to formers (M/F) ratio. The prepared compounds were characterized by X-ray diffraction. The impedance measurements were made on different Agl compositions of the SMA glasses as a function of frequency (6.5 Hz-65 kHz) and temperature (303-343 K), using the Solatron frequency-response analyser(model 1250). The bulk conductivity and the appropriate physical model (equivalent circuit) of the SMA glass were obtained from the impedance analysis. The a.c. conductivity was calculated for different Agl compositions of SMA glasses at various temperatures and the obtained a.c. conductivity results were analysed using Jonscher's Universal Law. The conduction mechanism for the highest conducting SMA glassy compound has been explained using the diffusion path model.