Nanocrystallisation and Nanoquasicrystallisation in (Ti/Hf)-Zr-(Ni/Cu) Ternary Alloys

The applicability of the confusion principle and size factor in glass formation has been explored by following different combinations of isoelectronic Ti, Zr and Hf metals. Four alloys of nominal composition Zr41.5Ti41.5Ni17, Zr41.5Hf41.5Ni17, Zr25Ti25Cu50 and Zr34Ti16Cu50 have been rapidly solidified to obtain an amorphous phase and their crystallisation behaviour has been studied. The Ti-Zr-Ni alloy crystallises in three steps. Initially this alloy precipitates icosahedral quasicrystalline phase, which on further heat treatment precipitates cF96 Zr2Ni phase. The Zr-Hf-Ni alloy can not be amorphised under the same experimental conditions. The amorphous Zr-Ti-Cu alloys at the initial stages of crystallisation phase-separateinto two amorphous phases and then on further heat treatment cF24 Cu5Zr and oC68 Cu10Zr7 phase are precipitated. The lower glass-forming abilityof Zr-Hf-Ni alloy and the crystallisation behaviour of the above alloys has been studied. The rationale behind nanoquasicrystallisation and the formation of other intermetallic phases has been explained.

Microstructure and mechanical properties of electron beam weld joints of a Zr41Ti14Cu12Ni10Be23 bulk metallic glass with Zr

The electron beam welding technique was used to join Zr41Ti14Cu12Ni10Be23 bulk metallic glass (BMG) to crystalline pure Zr. Compositional, microstructural, and mechanical property variations across the welded interface were evaluated. It is shown that a crystalline layer develops close to the welding interface. Transmission electron microscopy of this layer indicates the crystalline phase to be tetragonal with lattice parameters close to that reported for Zr2Ni. However, the composition of this phase is different as it contains other alloying additions. The interface layer close to the bulk metallic glass side contains nanocrystalline Zr2Cu phase embedded in the glassy matrix. Nanoindentation experiments indicate that the hardness of the crystalline layer, although less than the bulk metallic glass, is more than the Zr itself. Commensurately, tensile tests indicate that the failure of the welded samples occurs at the Zr side rather than at the weld joint.

The influence of Zr layer thickness on contact deformation and fracture in a ZrN-Zr multilayer coating

In order to understand the influence of ductile metal interlayer on the overall deformation behavior of metal/nitride multilayer, different configurations of metal and nitride layers were deposited and tested under indentation loading. To provide insight into the trends in deformation with multilayer spacings, an FEM model with elastic-perfect plastic metal layers alternate with an elastic nitride on top of an elastic-plastic substrate. The strong strain mismatch between the metal and nitride layers significantly alters the stress field under contact loading leading to micro-cracking in the nitride, large tensile stresses immediately below the contact, and a transition from columnar sliding in thin metal films to a more uniform bending and microcracking in thicker coatings.

Growth mechanism of the Nb(X)Si-2 and [Nb(X)](5)Si-3 phases by reactive diffusion in Nb (X = Ti, Mo, or Zr)-Si systems

The effects of Mo, Ti, and Zr on the diffusion and growth of the Nb(X)Si-2 and Nb(X)(5)Si-3 phases in an Nb(X)-Si system are analyzed. The integrated diffusion coefficients are determined from diffusion couple experiments and compared with the data previously calculated in a binary Nb-Si system. The growth rates of both phases are affected by the addition of Mo and Zr, whereas the addition of Ti has no effect. The atomic mechanism of diffusion is also discussed based on the crystal structure and the possible changes in the defect concentrations due to alloying. Finally, the growth mechanism of the phases is discussed on the basis of a physico-chemical approach. (C) 2011 Elsevier Ltd. All rights reserved.

Structure and Photocatalytic Activity of Ti 1- x M x O 2±δ (M = W, V, Ce, Zr, Fe, and Cu) Synthesized by Solution Combustion Method

The W, V, Ce, Zr, Fe, and Cu metal ion substituted nanocrystalline anatase TiO2 was prepared by solution combustion method and characterized by XRD, Raman, BET, EPR, XPS, IR TGA, UV absorption, and photoluminescence measurements. The structural studies indicate that the solid solution formation was limited to a narrow range of concentrations of the dopant ions. The photocatalytic degradation of 4-nitrophenol under UV and solar exposure was investigated with Ti1-xMxO2±δ. The degradation rates of 4-nitrophenol with these catalysts were lesser than the degradation rates of 4-nitrophenol with undoped TiO2 both with UV exposure and solar radiation. However, the photocatalytic activities of most metal ion doped TiO2 are higher than the activity of the commercial TiO2, Degussa P25. The decrease in photocatalytic activity is correlated with decrease in photoluminescence due to electron states of metal ions within the band gap of TiO2.

Synthesis, structure and photocatalytic activity of nano TiO2 and nano Ti1-xMxO2-delta (M = Cu, Fe, Pt, Pd, V, W, Ce, Zr)

We have synthesized 5-7 nm size, highly crystalline TiO2 which absorbs radiation in the visible region of solar spectrum. The material shows higher photocatalytic activity both in UV and visible region of the solar radiation compared to commercial Degussa P25 TiO2. Transition metal ion substitution for Ti4+ creates mid-gap, states which act as recombination centers for electron-hole induced by photons thus reducing photocatalytic activity. However, Pt, Pd and Cu ion substituted TiO2 are excellent CO oxidation and NO reduction catalysts at temperatures less than 100 degrees C.

Nanoindentation response of an ion irradiated Zr-based bulk metallic glass

Nanoindentation experiments were conducted on a Ni+ ion-irradiated Zr-based bulk metallic glass (BMG). The irradiation was carried out using 2.5, 5, 10 and 15 MeV ions and a flux of similar to 10(16) ions/cm(2). Post mortem imaging of the indents reveals a transition in the deformation mechanism of the irradiated regions from heterogeneous shear banding to homogeneous flow. Additionally, the load-displacement curves exhibit a transition from serrated to continuous flow with increasing severity of irradiation damage. The stress-strain response obtained from micro-pillar compression experiments complements the indentation response exhibiting a decrease in the flow stress and an `apparent' strain hardening at the lowest irradiation damage investigated, which is not observed in the as-cast alloy. (C) 2011 Elsevier B.V. All rights reserved.

Interdiffusion in Nb-Mo, Nb-Ti and Nb-Zr systems

Diffusion couple technique is used to study interdiffusion in Nb-Mo, Nb-Ti and Nb-Zr systems. Interdiffusion coefficients at different temperatures and compositions are determined using the relation developed by Wagner. The change in activation energy for interdiffusion with composition is determined. Further, impurity diffusion coefficient of the species are determined and compared with the available data in literature.

Room-temperature anelasticity and viscoplasticity of Cu-Zr bulk metallic glasses evaluated using nanoindentation

Anelastic and viscoplastic characteristics of Cu50Zr50 and Cu65Zr35 binary bulk metallic glasses at room temperature were examined through nanoindentation creep experiments. Results show that both the deformations are relatively more pronounced in Cu50Zr50 than in Cu65Zr35, and their amount increases with the loading rate. The results are analyzed in terms of the influences of structural defects and loading rate on the room temperature indentation creep.

Anomalous piezoelectric response due to stabilization of two ferroelectric phases in Zr-modified BaTiO3

The lead-free Ba (Ti1-xZrx)O-3 ceramic has shown enhanced piezo-response (d(33)) in a narrow composition interval (0.01 <= x <= 0.03) exhibiting the coexistence of two ferroelectric phases. The system presents two electric-field-dependent-property regimes: (i) a low field regime (E < 1.7 kV mm(-1)) where d(33) is nearly independent of the poling field, and (ii) (E > 1.7 kV mm(-1)) for which d(33) drops sharply. X-ray diffraction studies revealed that the later phenomenon is related to field driven irreversible structural transformation, which tends to drive the system away from an equilibrium two phase state to a nearly single phase metastable state.

Detailed investigation of contact deformation in ZrN/Zr multiplayer-understanding the role of volume fraction, bilayer spacing, and morphology of interfaces

A systematic study was done to understand the influence of volume fractions and bilayer spacings for metal/nitride multilayer coating using finite element method (FEM). An axisymmetric model was chosen to model the real situation by incorporating metal and substrate plasticity. Combinations of volume fractions and bilayer spacings were chosen for FEM analysis consistent with experimental results. The model was able to predict trends in cracking with respect to layer spacing and volume fraction. Metal layer plasticity is seen to greatly influence the stress field inside nitride. It is seen that the thicker metal induces higher tensile stresses inside nitride and hence leads to lower cracking loads. Thin metal layers < 10 nm were seen to have curved interfaces, and hence, the deformation mode was interfacial delamination in combination with edge cracking. There is an optimum seen with respect to volume fraction similar to 13% and metal layer thickness similar to 30 nm, which give maximum crack resistance.

Suppression of grain boundary relaxation in Zr-doped BiFeO3 thin films

Here, we present the results of temperature dependent dielectric studies on chemical solution processed Zr-doped BiFeO3 (BFO) thin films deposited on Pt/Si substrates. We find that in contrast to the undoped BFO films, Zr doping at Fe-site suppresses the low frequency dielectric relaxation originating from the grain boundaries, attributed to the increased dipolar rigidity due to stronger Zr-O bonds. Temperature dependent dc conductivity obtained from impedance and modulus analyses shows two distinct conduction processes occurring inside the grains. At temperature below similar to 423K, conductivity is nearly temperature independent, while in the high temperature regime (above similar to 423K), conduction is governed by the long range movement of oxygen vacancies with an activation energy of similar to 1eV. (C) 2014 AIP Publishing LLC.

Orthorhombic-tetragonal phase coexistence and enhanced piezo-response at room temperature in Zr, Sn, and Hf modified BaTiO3

The effect of Zr, Hf, and Sn in BaTiO3 has been investigated at close composition intervals in the dilute concentration limit. Detailed structural analysis by x-ray and neutron powder diffraction revealed that merely 2mol. % of Zr, Sn, and Hf stabilizes a coexistence of orthorhombic (Amm2) and tetragonal (P4mm) phases at room temperature. As a consequence, all the three systems show substantial enhancement in the longitudinal piezoelectric coefficient (d(33)), with Sn modification exhibiting the highest value similar to 425 pC/N. (C) 2014 AIP Publishing LLC.

Hydrogen-induced hardening and softening of Ni-Nb-Zr amorphous alloys: Dependence on the Zr content

The influence of absorbed hydrogen on the mechanical behavior of a series of Ni-Nb-Zr amorphous metallic ribbons was investigated through nanoindentation experiments. It was revealed that the influence is significantly dependent on Zr content, that is, hydrogen induced softening in relatively low-Zr alloys, whereas hydrogen induced hardening in high-Zr alloys. The results are discussed in terms of the different roles of mobile and immobile hydrogen in the plastic deformation. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Role of interface curvature on stress distribution under indentation for ZrN/Zr multilayer coating

Contact damage in curved interface nano-layeredmetal/nitride (150 (ZrN)/10 (Zr) nm) multilayer is investigated in order to understand the role of interface morphology on contact damage under indentation. A finite element method (FEM) model was formulated with different wavelengths of 1000 nm, 500 nm, 250 nm and common height of 50 nm, which gives insight on the effect of different curvature on stress field generated under indentation. Elastic-plastic properties were assigned to the metal layer and substrate while the nitride layer was assigned perfectly elastic properties. Curved interface multilayers show delamination along the metal/nitride interface and vertical cracks emanating from the ends of the delamination. FEM revealed the presence of tensile stress normal to the interface even under the contact, along with tensile radial stresses, both present at the valley part of the curve, which leads to vertical cracks associated with interfacial delamination. Stress enhancement was seen to be relatively insensitive to curvature. (C) 2014 Elsevier B.V. All rights reserved.