Wallner lines, crack velocity and mechanisms of crack nucleation and growth in a brittle bulk metallic glass

Mode I fracture experiments were conducted on brittle bulk metallic glass (BMG) samples and the fracture surface features were analyzed in detail to understand the underlying physical processes. Wollner lines, which result from the interaction between the propagating crack front and shear waves emanating from a secondary source, were observed on the fracture surface and geometric analysis of them indicates that the maximum crack velocity is similar to 800 m s(-1), which corresponds to similar to 0.32 times the shear wave speed. Fractography reveals that the sharp crack nucleation at the notch tip occurs at the mid-section of the specimens with the observation of flat and half-penny-shaped cracks. On this basis, we conclude that the crack initiation in brittle BMGs is stress-controlled and occurs through hydrostatic stress-assisted cavity nucleation ahead of the notch tip. High magnification scanning electron and atomic force microscopies of the dynamic crack growth regions reveal highly organized, nanoscale periodic patterns with a spacing of similar to 79 nm. Juxtaposition of the crack velocity with this spacing suggests that the crack takes similar to 10(-10) s for peak-to-peak propagation. This, and the estimated adiabatic temperature rise ahead of the propagating crack tip that suggests local softening, is utilized to critically discuss possible causes for the nanocorrugation formation. Taylor's fluid meniscus instability is unequivocally ruled out. Then, two other possible mechanisms, viz. (a) crack tip blunting and resharpening through nanovoid nucleation and growth ahead of the crack tip and eventual coalescence, and (b) dynamic oscillation of the crack in a thin slab of softened zone ahead of the crack-tip, are critically discussed. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Room temperature ferromagnetic and ferroelectric properties of Bi1-xCaxMnO3 thin films

Bi1-xCaxMnO3 (BCMO) thin films with x = 0, 0.1, 0.2, 0.3 and 0.4 are successfully deposited on the n-type Si (100) substrate at two different temperatures of 400 degrees C and 800 degrees C using RF magnetron sputtering. The stoichiometry of the films and oxidation state of the elements have been described by X-ray photoelectron spectroscopy analysis. Dielectric measurement depicts the insulating property of BCMO films. Magnetic and ferroelectric studies confirm the significant enhancement in spin orientation as well as electric polarization at room temperature due to incorporation of Ca2+ ions into BiMnO3 films. The BCMO (x = 0.2) film grown at 400 degrees C shows better magnetization (M-sat) and polarization (P-s) with the measured values of 869 emu / cc and 6.6 mu(C)/cm(2) respectively than the values of the other prepared films. Thus the realization of room temperature ferromagnetic and ferroelectric ordering in Ca2+ ions substituted BMO films makes potentially interesting for spintronic device applications. (C) 2014 Author(s).

A Reactive Intermediate, Ni-5(C6H4N3)(6)(CO)(4)], in the Formation of Nonameric Clusters of Nickel, Ni-9(C6H4N3)(12)(CO)(6)] and Ni-9(C6H4N3)(12)(CO)(6)].2(C3H7NO)

Three new molecular compounds, Ni-5(bta)(6)(CO)(4)], I, Ni-9(bta)(12)(CO)(6)], II, Ni-9(bta)(12)(CO)(6)]. 2(C3H7NO), III, (bta = benzotriazole) were prepared employing solvothermal reactions. Of these, I have pentanuclear nickel, whereas II and III have nonanuclear nickel species. The structures are formed by the connectivity between the nickel and benzotriazole giving rise to the 5- and 9-membered nickel clusters. The structures are stabilised by extensive pi aEuro broken vertical bar pi and C-H... pi interactions. Compound II and III are solvotamorphs as they have the same 9-membered nickel clusters and have different solvent molecules. To the best of our knowledge, the compounds I-III represent the first examples of the same transition element existing in two distinct coordination environment in this class of compounds. The studies reveal that compound I is reactive and could be an intermediate in the preparation of II and III. Thermal studies indicate that the compounds are stable upto 350(a similar to)C and at higher temperatures (similar to 800(a similar to)C) the compounds decompose into NiO. Magnetic studies reveal that II is anti-ferromagnetic.

Co-liposomes of redox-active alkyl-ferrocene modified low MW branched PEI and DOPE for efficacious gene delivery in serum

Herein, we present six new lipopolymers based on low molecular weight, branched polyethylenimine (BPEI 800 Da) which are hydrophobically modified using ferrocene terminated alkyl tails of variable lengths. The effects of degree of grafting, spacer length and the redox state of ferrocene in the lipopolymers on the self assembly properties were investigated in detail by TEM, AFM, DLS and zeta potential measurements. The assemblies displayed an oxidation induced increase in the size of the aggregates. The co-liposomes comprising the lipopolymer and a helper lipid, 1,2-dioleoyl phosphatidyl ethanolamine (DOPE), showed excellent gene (pDNA) delivery capability in a serum containing environment in two cancer cell lines (HeLa and U251 cells). Optimized formulations showed remarkably higher transfection activity than BPEI (25 kDa) and were also significantly better than a commercial transfection reagent, Lipofectamine 2000 as evidenced from both the luciferase activity and GFP expression analysis. Oxidation of ferrocene in the lipopolymers led to drastically reduced levels of gene transfection which was substantiated by reduced cellular internalization of fluorescently labelled pDNA as detected using confocal microscopy and flow cytometry. Moreover, the transfection inactive oxidized lipopolyplexes could be turned transfection active by exposure to ascorbic acid (AA) in cell culture medium during transfection. Endocytosis inhibition experiments showed that gene expression mediated by reduced formulations involved both clathrin and caveolae mediated pathways while the oxidized formulations were routed via the caveolae. Cytotoxicity assays revealed no obvious toxicity for the lipopolyplexes in the range of optimized transfection levels in both the cell lines studied. Overall, we have exploited the redox activity of ferrocene in branched PEI-based efficient polymeric gene carriers whose differential transfection activities could be harnessed for spatial or temporal cellular transfections.

High-Temperature Deformation Processing Map Approach for Obtaining the Desired Microstructure in a Multi-component (Ni-Ti-Cu-Fe) Alloy

An equiatomic NiTiCuFe multi-component alloy with simple body-centered cubic (bcc) and face-centered cubic solid-solution phases in the microstructure was processed by vacuum induction melting furnace under dynamic Ar atmosphere. High-temperature uniaxial compression experiments were conducted on it in the temperature range of 1073 K to 1303 K (800 degrees C to 1030 degrees C) and strain rate range of 10(-3) to 10(-1) s(-1). The data generated were analyzed with the aid of the dynamic materials model through which power dissipation efficiency and instability maps were generated so as to identify the governing deformation mechanisms that are operative in different temperature-strain rate regimes with the aid of complementary microstructural analysis of the deformed specimens. Results indicate that the stable domain for the high temperature deformation of the multi-component alloy occurs in the temperature range of 1173 K to 1303 K (900 degrees C to 1030 degrees C) and (epsilon) over dot range of 10(-3) to 10(-1.2) s(-1), and the deformation is unstable at T = 1073 K to 1153 K (800 degrees C to 880 degrees C) and (epsilon) over dot = 10(-3) to 10(-1.4) s(-1) as well as T = 1223 K to 1293 K (950 degrees C to 1020 degrees C) and (epsilon) over dot = 10(-1.4) to 10(-1) s(-1), with adiabatic shear banding, localized plastic flow, or cracking being the unstable mechanisms. A constitutive equation that describes the flow stress of NiTiCuFe multi-component alloy as a function of strain rate and deformation temperature was also determined. (C) The Minerals, Metals & Materials Society and ASM International 2015

Structural and functional analysis of two universal stress proteins YdaA and YnaF from Salmonella typhimurium: possible roles in microbial stress tolerance

In many organisms ``Universal Stress Proteins'' CUSPS) are induced in response to a variety of environmental stresses. Here we report the structures of two USPs, YnaF and YdaA from Salmonella typhimurium determined at 1.8 angstrom and 2.4 angstrom resolutions, respectively. YnaF consists of a single USP domain and forms a tetrameric organization stabilized by interactions mediated through chloride ions. YdaA is a larger protein consisting of two tandem USP domains. Two protomers of YdaA associate to form a structure similar to the YnaF tetramer. YdaA showed ATPase activity and an ATP binding motif G-2X-G-9X-G(S/T/N) was found in its C-terminal domain. The residues corresponding to this motif were not conserved in YnaF although YnaF could bind ATP. However, unlike YdaA, YnaF did not hydrolyse ATP in vitro. Disruption of interactions mediated through chloride ions by selected mutations converted YnaF into an ATPase. Residues that might be important for ATP hydrolysis could be identified by comparing the active sites of native and mutant structures. Only the C-terminal domain of YdaA appears to be involved in ATP hydrolysis. The structurally similar N-terminal domain was found to bind a zinc ion near the segment equivalent to the phosphate binding loop of the C-terminal domain. Mass spectrometric analysis showed that YdaA might bind a ligand of approximate molecular weight 800 daltons. Structural comparisons suggest that the ligand, probably related to an intermediate in lipid A biosynthesis, might bind at a site close to the zinc ion. Therefore, the N-terminal domain of YdaA binds zinc and might play a role in lipid metabolism. Thus, USPs appear to perform several distinct functions such as ATP hydrolysis, altering membrane properties and chloride sensing. (C) 2015 Elsevier Inc. All rights reserved.

All Digital Energy Sensing for Minimum Energy Tracking

Minimizing energy consumption is of utmost importance in an energy starved system with relaxed performance requirements. This brief presents a digital energy sensing method that requires neither a constant voltage reference nor a time reference. An energy minimizing loop uses this to find the minimum energy point and sets the supply voltage between 0.2 and 0.5 V. Energy savings up to 1275% over existing minimum energy tracking techniques in the literature is achieved.

ADAPTATION OF MW LEVEL NATURAL GAS LEAN BURN ENGINE FOR PRODUCER GAS OPERATION A GRID CONNECTED POWER PLANT

Availability of producer gas engines at MW being limited necessitates to adapt engine from natural gas operation. The present work focus on the development of necessary kit for adapting a 12 cylinder lean burn turbo-charged natural gas engine rated at 900 kWe (Waukesha make VHP5904LTD) to operate on producer and set up an appropriate capacity biomass gasification system for grid linked power generation in Thailand. The overall plant configuration had fuel processing, drying, reactor, cooling and cleaning system, water treatment, engine generator and power evacuation. The overall project is designed for evacuation of 1.5 MWe power to the state grid and had 2 gasification system with the above configuration and 3 engines. Two gasification system each designed for about 1100 kg/hr of woody biomass was connected to the engine using a producer gas carburetor for the necessary Air to fuel ratio control. In the use of PG to fuel IC engines, it has been recognized that the engine response will differ as compared to the response with conventional fueled operation due to the differences in the thermo-physical properties of PG. On fuelling a conventional engine with PG, power de-rating can be expected due to the lower calorific value (LCV), lower adiabatic flame temperature (AFT) and the lower than unity product to reactant more ratio. Further the A/F ratio for producer gas is about 1/10th that of natural gas and requires a different carburetor for engine operation. The research involved in developing a carburetor for varying load conditions. The patented carburetor is based on area ratio control, consisting of a zero pressure regulator and a separate gas and air line along with a mixing zone. The 95 litre engine at 1000 rpm has an electrical efficiency of 33.5 % with a heat input of 2.62 MW. Each engine had two carburetors designed for producer gas flow each capable of handling about 1200 m3/hr in order to provide similar engine heat input at a lower conversion efficiency. Cold flow studies simulating the engine carburetion system results showed that the A/F was maintained in the range of 1.3 +/- 0.1 over the entire flow range. Initially, the gasification system was tested using woody biomass and the gas composition was found to be CO 15 +/- 1.5 % H-2 22 +/- 2% CH4 2.2 +/- 0.5 CO2 11.25 +/- 1.4 % and rest N-2, with the calorific value in the range of 5.0 MJ/kg. After initial trials on the engine to fine tune the control system and adjust various engine operating parameter a peak load of 800 kWe was achieved, while a stable operating conditions was found to be at 750 kWe which is nearly 85 % of the natural gas rating. The specific fuel consumption was found to be 0.9 kg of biomass per kWh.

Photo induced effects on the optical properties of As20Sb20S60 thin films

The thermally evaporated As20Sb20S60 amorphous film of 800 nm thickness was subjected to light exposure for photo induced studies. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS spectra and Raman shift supports the optical changes happening in the film due to light exposure.

A Na/MnO2 Primary Cell Employing Poorly Crystalline MnO2

Presently Li/MnO2 is one of the widely used primary battery for a variety of applications. As the global resources for Na are plentiful in relation to those for Li, Na/MnO2 primary battery is expected to be an economical, viable alternate to Li/MnO2 system. But marginal inferior properties of Na/MnO2, which arise due to the differences in properties between Li and Na, are inevitable. In the present work, Na/MnO2 and Li/MnO2 laboratory scale primary cells in non-aquebus electrolytes are assembled and their electrochemical properties are studied in similar experimental conditions. The MnO2 used for these studies is prepared from KMnO4 and it is in amorphous state. The discharge behavior of Na/MnO2 cell is similar to that of Li/MnO2 cell, but with nominal voltage less by about 0.35 V, as expected. The specific capacity of amorphous MnO2 is 300 mAh g(-1) in both Na/MnO2 and Li/MnO2 cells. On heating the as prepared amorphous MnO2 at temperature range 300-800 degrees C, it converts to crystalline ct-MnO2. The capacity of crystalline MnO2 is significantly less than the amorphous MnO2. The results suggest that Na/MnO2 is a viable, economical alternate to Li/MnO2 primary cell. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Piezoelectric properties of individual nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 obtained by oxalate precursor route

Nanocrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) powder was synthesized via the complex oxalate precursor route at a relatively low temperature (800 degrees C/5 h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier transform infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was corroborated by Raman study. Transmission electron microscopy (TEM) carried out on 800 degrees C and 1000 degrees C/5 h heat treated BCZT powder revealed the crystallite size to be in the range of 20-50 nm and 40-200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 +/- 0.02 eV and 3.03 +/- 0.02 eV respectively for 800 degrees C (20-50 nm) and 1000 degrees C/5 h (40-200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using a piezoresponse force microscope (PFM). The d(33) coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm V-1 and 47 pm V-1 respectively. These were superior to that of BaTiO3 nanocrystal (approximate to 50 nm) and promising from a technological/industrial applications viewpoint.

Panchromatic Borane-aza-BODIPY Conjugate: Synthesis, Intriguing Optical Properties, and Selective Fluorescent Sensing of Fluoride Anions

A new triarylborane-aza-BODIPY conjugate is reported. The compound consists of two blue emissive dimesitylarylborane moieties and a near-infrared (NIR) emissive aza-BOIDPY core and shows panchromatic absorption spanning approximately 300-800 nm. DFT computational studies suggest limited electronic communication between the individual fluorophore units. Hence, the partial energy transfer from blue fluorophore triarylborane to NIR chromophore aza-BODIPY unit leads to a broad dual-emissive feature covering a large part of visible and NIR region. Furthermore, the broadband emissive compound can act as a selective sensor for fluoride anion as a result of fluorescence quenching response in both visible and NIR spectral regions.

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.

Low thermal conductivity of endogenous manganese silicide/Si composites for thermoelectricity

Higher manganese silicide (HMS) based alloys with eutectic composition (Si-33.3 at% Mn) were prepared by arc-melting, melt-spinning and ball milling in order to evaluate the effect of microstructure on the thermal conductivity. Powder X-ray diffraction, SEM, EPMA and TEM analysis confirmed the presence of Si as a secondary phase distributed in the HMS matrix phase. Thermal properties of the samples were studied in the temperature range of 300-800 K. The microstructure refinement resulting from ball milling leads to a decrease of the thermal conductivity from 4.4 W/mK to 1.9 W/mK, whereas meltspinning is inefficient to this respect. The results show an opportunity to produce bulk higher manganese silicide alloys with reduced thermal conductivity in order to enhance its thermoelectric performance. (C) 2015 Elsevier B.V. All rights reserved.

Effect of laser irradiation on the optical properties of As40Sb15Se45 chalcogenide thin films

The exposure with band gap light of thermally evaporated As40Sb15Se45 amorphous film of 800 nm thickness, were found to be accompanied by optical changes. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS spectra and Raman shift supports the optical changes happening in the film due to light exposure.