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.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Ferroelectric instabilities and enhanced piezoelectric response in Ce modified BaTiO3 lead-free ceramics

The crystal structure, ferroelectric, and piezoelectric behaviors of the Ba(Ti1-xCex)O-3 solid solution have been investigated at close composition intervals in the dilute concentration regime. Ce concentration as low as 2 mol. % induces tetragonal-orthorhombic instability and coexistence of the phases, leading to enhanced high-field strain and direct piezoelectric response. Detailed structural analysis revealed tetragonal + orthorhombic phase coexistence for x = 0.02, orthorhombic for 0.03 <= x <= 0.05, and orthorhombic + rhombohedral for 0.06 <= x <= 0.08. The results suggest that Ce-modified BaTiO3 is a potential lead-free piezoelectric material. (C) 2015 AIP Publishing LLC.

Anodization of sputtered metallic films: The microstructural connection

A simple microstructural rationale for successful anodization of metallic films into ordered oxide nanostructures has been identified. It applies to three of the most commonly studied systems, Zr, Ti and Al films and can be extended to other such oxides. A dense Zone T or II microstructure, in sputtered films, is the most critical ingredient. While T-substrate > 0.3T(melting) Ching is the simplest route, pressure and plasma heating can also be exploited. Such microstructures are also associated with a unique growth stress signature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Hydrothermal preparation of Ba(Ti,Zr)O3 fine powders

Fine powders consisting of aggregated submicron crystallites of Ba(Ti,Zr)O3 in the complete range of Ti/Zr ratios are prepared at 85–130°C by hydrothermal method, starting from TiO2 + ZrO2 · xH2O mixed gel and Ba(OH)2 solution. The products obtained below 110°C incorporate considerable amounts of H2O and OH− within the lattice. As-prepared BaTiO3 is cubic and converts to tetragonal phase after the heat treatment at 1200°C, accompanied by the loss of residual hydroxyl ions. TEM investgations of the growth features show a transformation of the gel to the crystallite. Ba2+ ions entering the gel produce chemical changes within the gel, followed by dehydration, resulting in a cubic perovskite phase irrespective of Ti/Zr. The sintering properties of these powders to fine-grained, high density ceramics and their dielectric properties are presented.

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.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.

Formation of Pb(Ti,Zr)O3, from thermal decomposition of oxalate precursors

Lead zir conyl oxalate hexahydrate (LZO) and lead titanyl zirconyl oxalate hydrate (LTZO) are prepared and characterized. Their thermal decompositions have been investigated by thermoanalytical and gas analysis techniques. The decomposition in air or oxygen has three steps — dehydration, decomposition of the oxalate to a carbonate and the decomposition of carbonate to PbZrO3. In non oxidising atmosphere, partial reduction of Pb(II) to Pb(0) takes place at the oxalate decomposition step. The formation of free metallic lead affects the stoichiometry of the intermediate carbonate and yields a mixture of Pb(Ti,Zr)O3 and ZrO2 as the final products. By maintaining oxidising atmosphere and low heating rate, direct preparation of stoichiometric, crystalline Pb(Ti,Zr)O3 at 550°C is possible from the corresponding oxalate precursor.

Formation ranges of icosahedral, amorphous and crystalline phases in rapidly solidified Ti-Zr-Hf-Ni alloys

From the quaternary Ti-Zr-Hf-Ni phase diagram. the cross-section at 20 at % Ni was selected for investigation. The icosahedral quasicrystalline, crystalline and amorphous phases were observed to form in nine kinds of rapidly solidified (TixZryHfz)(80)Ni-20 (x + y + z = 1) alloys at different compositions. The quasilattice constants of 0.519 and 0.531 nm were obtained for the icosahedral phase formed in the melt-spun Ti40Zr20Hf20Ni20 and Ti20Zr40Hf20Ni20 alloys. respectively. The icosahedral phase formed in the melt-spun Ti40Zr20Hf20Ni20 alloy especially is thermodynamically stable. The supercooled liquid region of the Ti20Zr20Hf40Ni20 glassy alloy reached 64 K. From these results a comparison of quasicrystal-forming and glass-forming abilities, was carried out. The quasicrystal-forming ability was reduced and glass-forming ability was improved with an increase in Hf and Zr contents in the (TixZryHfz)(80)Ni-20 alloys. On the other hand. an increase in Ti content caused an improvement in quasicrystal-forming ability.

Stability of Fe3+ -VO defect pairs in polycrystalline Pb(Ti,Zr)O3

The intensity of the EPR signal with g = 5.985 arising from a ferric ion â oxygen vacancy defect pair (Fe3+ â VO) in PbTiO3, varies with the extent of PbO nonstoichiometry at constant Fe3+ content due to an increased oxygen vacancy concentration. In PZT solid solutions, the signal intensity decreases with an increase in Zr. A lower intensity is also noticed for Fe3+ â VO signals in PbZrO3. This behaviour is explained on the basis of PbO nonstoichiometry arising from independent Pb- and O-vacancies as well as the randomly distributed crystallographic shear (CS) plane defects. The contribution to PbO nonstoichiometry from CS planes is larger in high zirconium compositions of PZT.

Hydrothermal synthesis of Ba(Ti, Sn)O3 fine powders and dielectric properties of the corresponding ceramics

Fine powders of submicron-sized crystallites of BaTiO3 were prepared at 85–130°C by the hydrothermal method, starting from TiO2.ξH2O gel and Ba(OH)2 solution. The products obtained below 110°C incorporated considerable amounts of H2O and OH− in the lattice. As-prepared BaTiO3 is cubic and converts to the tetragonal phase after heat treatment at 1200°C, accompanied by the loss of residual OH− ions. Hydrothermal reaction of SnO2.ξH2O gel with Ba(OH)2 at 150–260°C gives rise to the hydrated phase, BaSn(OH)6.3H2O, due to the amphoteric nature of SnO2.ξH2O which stabilises Sn(OH)62− anions in basic media. On heating in air or releasing the pressure in situ at 260°C, BaSn(OH)6.3H2O converts to BaSnO3 through an intermediate, BaSnO(OH)4. Solid solutions of Ba(Ti,Sn)O3 are directly formed from (TiO2 + SnO2)..ξH2O gel up to 35 mol% SnO2. At higher Sn contents, the hydrothermal products are mixtures of BaSn(OH)6.3H2O and BaTiO3, which on annealing at 1000°C result in monophasic Ba(Ti,Sn)O3. The sintering characteristics and the dielectric properties of the ceramics prepared out of these fine powders are presented. The dielectric properties of fine-grained Ba(Ti,Sn)O3 ceramics are explained on the basis of the prevailing diffuse phase transition behaviour.

TlCaBa2Cu2O7: The 1122 (90 K) superconductor in the new Tl(Ca,Ba)n+1CunO2n+3 seriesstar, open

The 1122 (n=2) member of the Tl(Ca,Ba)n+1CunO2n+3 series containing a single Tl-O layer is shown to be associated with a Tc of 90 K. This value of Tc is significantly lower than that of the 2122 phase (Tcnot, vert, similar110 K) with two Tl-O layers.

Are Metallocene-Acetylene (M = Ti, Zr, Hf) Complexes Aromatic Metallacyclopropenes?

The bonding nature of metallocene acetylene complexes Cp2M(eta(2)-H3SiC2SiH3) 1M and CP2M (eta(2)- HC2H) 1M' (M = Ti, Zr, Hf) wits studied by density functional theory method. It is found that this acetylene complex has indeed it metallacyclopropene moiety with two in-plane M-C sigma-bonds and one out-of-plane pi-bond interacting with the metal center, resulting in the formation of it delocalized three-center and two-electron (3c-2e) system. Along with its delocalized out-of-plane bonding, this complex has been characterized its aromatic on the basis of the computed stabilizing energy and negative nucleus-independent chemical shifts (NICS). The aromatic stabilization increases from Ti to Zr and Hf, and this is because of the increased charge separation between the CP2M fragment and the H3SiC2SiH3 (also HC2H) unit. The decrease of the M-C bond length from Zr to Hf is ttributed to the increased s character of both M and C hybridization of the M-C a-bonds.

Manifestation of geometric frustration on magnetic and thermodynamic properties of the pyrochlores Sm2X2O7 (X=Ti,Zr)

We present here magnetization, specific heat, and Raman studies on single-crystalline specimens of the first pyrochlore member Sm2Ti2O7 of the rare-earth titanate series. Its analogous compound Sm2Zr2O7 in the rare-earth zirconate series is also investigated in the polycrystalline form. The Sm spins in Sm2Ti2O7 remain unordered down to at least T=0.5 K. The absence of magnetic ordering is attributed to very small values of exchange (θcw∼−0.26 K) and dipolar interaction (μeff∼0.15 μB) between the Sm3+ spins in this pyrochlore. In contrast, the pyrochlore Sm2Zr2O7 is characterized by a relatively large value of Sm-Sm spin exchange (θcw∼−10 K); however, long-range ordering of the Sm3+ spins is not established at least down to T=0.67 K due to frustration of the Sm3+ spins on the pyrochlore lattice. The ground state of Sm3+ ions in both pyrochlores is a well-isolated Kramers doublet. The higher-lying crystal field excitations are observed in the low-frequency region of the Raman spectra of the two compounds recorded at T=10 K. At higher temperatures, the magnetic susceptibility of Sm2Ti2O7 shows a broad maximum at T=140 K, while that of Sm2Zr2O7 changes monotonically. Whereas Sm2Ti2O7 is a promising candidate for investigating spin fluctuations on a frustrated lattice, as indicated by our data, the properties of Sm2Zr2O7 seem to conform to a conventional scenario where geometrical frustration of the spin excludes their long-range ordering.

Studies on the ionic transport and structural investigations of La0.5Li0.5TiO3 perovskite synthesized by wet chemical methods and the effect of Ce, Zr substitution at Ti site

La0.5Li0.5TiO3 perovskite was synthesized by various wet chemical methods. By adopting low temperature methods of preparation lithium loss from the material is prevented. La0.5Li0.5TiO3 (LLTO) was formed with cubic symmetry at 1473 K. LLTO was formed at relatively lower temperature by using hydrothermal preparation method. PVA gel-decomposition route yield tetragonal LLTO on annealing the dried gel at 1473 K. By using gel-carbonate route LiTi2O4 minor phase was found to remain even after heat-treatment at 1473 K. The hydroxylation of LLTO was done in deionized water as well as in dilute acetic acid medium. By hydroxylation process incorporation of hydroxyls and leaching out of Li+ was observed from the material. The Li+ concentration of these compositions was examined by AAS. The electrical conductivities of these compositions were measured by dc and ac impedance techniques at elevated temperatures. The activation energies of electrical conduction for these compositions were estimated from the experimental results. The measured activation energy of Li+ conduction is 0.34 eV. Unhydroxylated samples exhibit only Li+ conduction, whereas, the hydroxylated LLTO show proton conductivity at 298-550 K in addition to Li+ conductivity. The effect of Zr or Ce substitution in place of Ti were attempted. La0.5Li0.5ZrO3 Perovskite was not formed; instead pyrochlore phase (La2Zr2O7) along with monoclinic ZrO2 phases was observed above 1173 K; below 1173 K cubic ZrO2 is stable. (La0.5Li0.5)(2)CeO4 solid solution was formed in the case of Ce substitution at Ti sublattice on heat-treatment up to 1673 K. (c) 2005 Springer Science + Business Media, Inc.