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.

Structural and magnetic properties of Dy3+ doped Y3Fe5O12 for microwave devices

The Dy3+ doped Y3-xDyxFe5O12 (x=0-3) nanopowders were prepared using microwave hydrothermal route. The structural and morphological studies were analyzed using transmission electron microscope, X-ray diffractometer and field emission scanning electron microscope. The nanopowders were sintered at 900 degrees C/90 min using microwave furnace. Dense ceramics with theoretical density of around 95% was obtained. Ferro magnetic resonance (FMR) spectrum and microwave absorption spectrum of Dy3+ doped YIG were studied, the signal exhibits a resonance character for all Dy3+ variations. It was observed that the location of the FMR signal peak at the field axes monotonically shifts to higher field with increasing Dy3+ content. The dielectric and magnetic properties (epsilon', epsilon `', mu' and mu `') of Dy3+ doped YIG were studied over a wide range of frequency (1-50 GHz). With increase of Dy3+ both epsilon' and mu' decreased. The low values of dielectric, magnetic properties and broad distribution of FMR line width of these ceramics are opening the real opportunity to use them for microwave devices above K- band frequency. (C) 2015 Elsevier Ltd. All rights reserved.

Dynamic compression behavior of reactive spark plasma sintered ultrafine grained (Hf, Zr)B-2-SiC composites

This paper reports the dynamic compression behavior of ultrafine grained (Hf, Zr)B-2-SiC composites, sintered using reactive spark plasma sintering at 1600 degrees C for 10 min. Dynamic strength of similar to 2.3 GPa has been measured using Split Hopkinson Pressure Bar (SHPB) tests in a reproducible manner at strain rates of 800-1300 s(-1). A comparison with competing boride based armor ceramics, in reference to the spectrum of properties evaluated, establishes the potential of (Hf, Zr)B-2-SiC composites for armor applications. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Optical and dielectric study of strontium modified barium zirconium titanate ceramic prepared by high energy ball milling

Strontium modified barium zirconium titanate with general formula Ba1-xSrxZr0.05Ti0.95O3 ceramics have been prepared by solid state and high energy ball milling technique. The X-ray diffraction and Rietveld refinement studies show that all the compositions have single phase symmetry. The composition BaZr0.05Ti0.95O3 shows orthorhombic symmetric with space group Amm2. The structure changes from orthorhombic to tetragonal with strontium doping up to x = 0.3 and with further addition, changes to cubic. The scanning electron micrographs show that the grain size decreases with increase in strontium content. The temperature dependent dielectric behavior shows three phase transition in the parent material which merges with an increase in Sr content The transition temperature and dielectric constant decreases with an increase in Sr concentration. The phase transition becomes more diffused with increment in doping concentration. The ferroelectric behavior of the ceramics is studied by the hysteresis loop. The optical behavior is studied by the UV-visible spectroscopy and found that the optical band gap increases with Sr concentration. (C) 2015 Elsevier B.V. All rights reserved.

Origin of room temperature weak-ferromagnetism in antiferromagnetic Pb(Fe2/3W1/3)O-3 ceramic

We report the origin of room temperature weak ferromagnetic behavior of polycrystalline Pb(Fe2/3W1/3)O-3 (PFW) powder. The structure and magnetic properties of the ceramic powder prepared by a Columbite method were characterized by X-ray and neutron diffraction, Mossbauer spectroscopy and magnetization measurements. Rietveld analysis of diffraction data confirm the formation of single phase PFW, without traces of any parasitic pyrochlore phase. PFW was found to crystallize in the cubic structure at room temperature. The Rietveld refinement of neutron diffraction data measured at room temperature confirmed the G-type antiferromagnetic structure of PFW in our sample. However, along with the antiferromagnetic (AFM) ordering of the Fe spins, we have observed the existence of weak ferromagnetism at room temperature through: (i) a clear opening of hysteresis (M-H) loop, (ii) bifurcation of the field cooled and zero-field cooled susceptibility; supported by Mossbauer spectroscopy results. The P-E loop measurements showed a non-linear slim hysteresis loop at room temperature due to the electronic conduction through the local inhomogeneities in the PFW crystallites and the inter-particle regions. By corroborating all the magnetic measurements, especially the spin glass nature of the sample, with the conduction behavior of the sample, we report here that the observed ferromagnetism originates at these local inhomogeneous regions in the sample, where the Fe-spins are not perfectly aligned antiferromagnetically due to the compositional disordering. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)(3) polysulphate: 3.8V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

Nanoparticle induced miscibility in LCST polymer blends: critically assessing the enthalpic and entropic effects

The use of copolymer and polymer blends widened the possibility of creating materials with multilayered architectures. Hierarchical polymer systems with a wide array of micro and nanostructures are generated by thermally induced phase separation (TIPS) in partially miscible polymer blends. Various parameters like the interaction between the polymers, concentration, solvent/non-solvent ratio, and quenching temperature have to be optimized to obtain these micro/nanophase structures. Alternatively, the addition of nanoparticles is another strategy to design materials with desired hetero-phase structures. The dynamics of the polymer nanocomposite depends on the statistical ordering of polymers around the nanoparticle, which is dependent on the shape of the nanoparticle. The entropic loss due to deformation of polymer chains, like the repulsive interactions due to coiling and the attractive interactions in the case of swelling has been highlighted in this perspective article. The dissipative particle dynamics has been discussed and is correlated with the molecular dynamics simulation in the case of polymer blends. The Cahn Hillard Cook model on variedly shaped immobile fillers has shown difference in the propagation of the composition wave. The nanoparticle shape has a contributing effect on the polymer particle interaction, which can change the miscibility window in the case of these phase separating polymer blends. Quantitative information on the effect of spherical particles on the demixing temperature is well established and further modified to explain the percolation of rod shaped particles in the polymer blends. These models correlate well with the experimental observations in context to the dynamics induced by the nanoparticle in the demixing behavior of the polymer blend. The miscibility of the LCST polymer blend depends on the enthalpic factors like the specific interaction between the components, and the solubility product and the entropic losses occurring due to the formation of any favorable interactions. Hence, it is essential to assess the entropic and enthalpic interactions induced by the nanoparticles independently. The addition of nanoparticles creates heterogeneity in the polymer phase it is localized. This can be observed as an alteration in the relaxation behavior of the polymer. This changes the demixing behavior and the interaction parameter between the polymers. The compositional changes induced due to the incorporation of nanoparticles are also attributed as a reason for the altered demixing temperature. The particle shape anisotropy causes a direction dependent depletion, which changes the phase behavior of the blend. The polymer-grafted nanoparticles with varying grafting density show tremendous variation in the miscibility of the blend. The stretching of the polymer chains grafted on the nanoparticles causes an entropy penalty in the polymer blend. A comparative study on the different shaped particles is not available up to date for understanding these aspects. Hence, we have juxtaposed the various computational studies on nanoparticle dynamics, the shape effect of NPs on homopolymers and also the cases of various polymer blends without nanoparticles to sketch a complete picture on the effect of various particles on the miscibility of LCST blends.

Strength reliability and in vitro degradation of three-dimensional powder printed strontium-substituted magnesium phosphate scaffolds

Strontium ions (Sr2+) are known to prevent osteoporosis and also encourage bone formation. Such twin requirements have motivated researchers to develop Sr-substituted biomaterials for orthopaedic applications. The present study demonstrates a new concept of developing Sr-substituted Mg-3(PO4)(2) - based biodegradable scaffolds. In particular, this work reports the fabrication, mechanical properties with an emphasis on strength reliability as well as in vitro degradation of highly biodegradable strontium-incorporated magnesium phosphate cements. These implantable scaffolds were fabricated using three-dimensional powder printing, followed by high temperature sintering and/or chemical conversion, a technique adaptable to develop patient-specific implants. A moderate combination of strength properties of 36.7 MPa (compression), 242 MPa (bending) and 10.7 MPa (tension) were measured. A reasonably modest Weibull modulus of up to 8.8 was recorded after uniaxial compression or diametral tensile tests on 3D printed scaffolds. A comparison among scaffolds with varying compositions or among sintered or chemically hardened scaffolds reveals that the strength reliability is not compromised in Sr-substituted scaffolds compared to baseline Mg-3(PO4)(2). The micro-computed tomography analysis reveals the presence of highly interconnected porous architecture in three-dimension with lognormal pore size distribution having median in the range of 17.74-26.29 mu m for the investigated scaffolds. The results of extensive in vitro ion release study revealed passive degradation with a reduced Mg2+ release and slow but sustained release of Sr2+ from strontium-substituted magnesium phosphate scaffolds. Taken together, the present study unequivocally illustrates that the newly designed Sr-substituted magnesium phosphate scaffolds with good strength reliability could be used for biomedical applications requiring consistent Sr2+-release, while the scaffold degrades in physiological medium. Statement of significance The study investigates the additive manufacturing of scaffolds based on different strontium-substituted magnesium phosphate bone cements by means of three-dimensional powder printing technique (3DPP). Magnesium phosphates were chosen due to their higher biodegradability compared to calcium phosphates, which is due to both a higher solubility as well as the absence of phase changes (to low soluble hydroxyapatite) in vivo. Since strontium ions are known to promote bone formation by stimulating osteoblast growth, we aimed to establish such a highly degradable magnesium phosphate ceramic with an enhanced bioactivity for new bone ingrowth. After post-processing, mechanical strengths of up to 36.7 MPa (compression), 24.2 MPa (bending) and 10.7 MPa (tension) could be achieved. Simultaneously, the failure reliability of those bioceramic implant materials, measured by Weibull modulus calculations, were in the range of 4.3-8.8. Passive dissolution studies in vitro proved an ion release of Mg2+ and PO43- as well as Sr2+, which is fundamental for in vivo degradation and a bone growth promoting effect. In our opinion, this work broadens the range of bioceramic bone replacement materials suitable for additive manufacturing processing. The high biodegradability of MPC ceramics together with the anticipated promoting effect on osseointegration opens up the way for a patient-specific treatment with the prospect of a fast and complete healing of bone fractures. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.