Search

The steady-state magneto-mechanical response of a magnetorheological fluid (MRF), prepared by dispersing 40 wt % of magnetically soft, light-weight coral-network-shaped yttrium iron garnet (YIG; Y3Fe5O12) powder in silicone oil (140 cSt) is studied as a function of shear rate, under different applied magnetic fields (B). The results show that the yield strength (tau(Y)) and viscosity (eta) of the MRF increase with B, and are strongly influenced by the physical parameters of the particles such as morphology and saturation magnetization. The low density of the YIG-particles, leading to higher volume fraction for equal mass loading, results in a higher viscosity in the absence of a magnetic field, in comparison to that of conventional metallic Fe-particle-based MRFs. Due to this, there is a relatively smaller increase in tau(Y) and eta when the magnetic field is switched on. The YIG-particles-based MRF has the advantages of high chemical stability, thermo-oxidative resistance and low-cost.

We report the phase-composition, structure and magnetic properties of two representative samples of naturally available iron-oxide containing ores/soils collected from two different regions in Karnataka, India. Presence of elements such as Fe, Si, Al and O were identified in both the samples using energy dispersive analysis of X-rays (EDAX). X-ray diffraction results confirmed that different ceramic phases such as crystalline iron oxide phases (Fe3O4, γ-Fe2O3 and α-Fe2O3), aluminosilicates (Al2SiO5) and low-quartz (SiO2) phases constitute the soil. The presence of ferrimagnetic phases (Fe3O4, γ-Fe2O3) makes the soil respond to a permanent magnet. Separation between the magnetic and non-magnetic phases was performed using a permanent magnet. The non-magnetic part of the sample contains a high amount of α-Fe2O3 phase along with aluminosilicates and low-quartz. The magnetic phases were further characterized and quantified. The presence of Fe3O4 phase in the samples was confirmed from the Verwey transition observed by internal-field NMR spectroscopy. Our results demonstrate that internal-field NMR and Mössbauer spectroscopy are complementary tools for characterizing iron containing soils. Furthermore, we found that the soil collected from the low temperature region (Sandur) contains more amounts of ferrimagnetic oxide (Fe3O4, γ-Fe2O3) phases, whereas the high temperature region (Hospete) contains more α-Fe2O3 phase. Hence, our results confirm that the phase composition of the soil is intimately related to the local daily temperature. Keywords: Iron ores, Phase composition, Magnetic properties, Internal field NMR, Mössbauer spectroscopy

Layered sodium iron phosphate phase [Na3Fe3(PO4)4] was synthesized by solution combustion synthesis method, marking the first attempt of solvothermal synthesis of this phase. Its crystal structure was verified by synchrotron and neutron powder diffraction. Rietveld analyses proved the phase purity and formation of monoclinic framework with C2/c symmetry. It undergoes an antiferromagnetic ordering ∼27 K. This combustion prepared nanoscale Na3Fe3(PO4)4 compound was found to be electrochemically active with a stepwise voltage profile involving an Fe3+/Fe2+ redox activity centred at 2.43 V vs. Na/Na+. Despite various cathode optimization, only 1.8 Na+ per formula unit could be reversibly inserted into the Na3Fe3(PO4)4 framework leading to capacity close to 50 mAh g−1. This limited electrochemical activity can be rooted to (i) relatively large diffusion barrier (ca. 0.28 eV) as per Bond valence site energy (BVSE) calculations and (ii) possible structural instability during (de)sodiation reaction.

Among ultra high temperature ceramics (UHTCs), ZrB2-based ceramics have received the most attention for applications in hypersonic space vehicles. However, UHTCs encounter several challenges pertaining to their processing to achieve the desired properties in order to optimally exploit their potential. In this perspective, the present work illustrates some of the sintering related challenges using a case study of ZrB2-SiC based ceramics. Multi stage spark plasma sintering is carried out on ZrB2-SiC based ceramics at 1500 degrees C with metallic Titanium as sinter-aid. High hardness of up to 28 GPa is obtained in dense ceramics with finer microstructure. Furthering towards design and fabrication of real scale hypersonic application such as thermal protection system, efforts have been taken to prove the scalability of the ceramics by consolidating up to phi 100 mm ceramic discs.

We report the steady-state shear response of polydisperse Ni-Zn ferrite-submicrospheres-based magnetorheological fluids (MRFs). The Ni-Zn ferrite spherical particles were prepared by solvothermal method. MRFs of three different concentrations (10, 20 and 40 wt%) were prepared by dispersing Ni-Zn ferrite submicrospheres in silicone oil. These MRFs were subjected to steady-state shear conditions, at different applied magnetic fields. Dynamic yield strength values corresponding to different applied field strengths showed increase in value with increase in magnetic field strength. Furthermore, the dynamic yield strength scaled up with the concentration of Ni-Zn ferrite spherical particles in the carrier fluid. Comparison of the dynamic yield strengths for the MRFs showed that the values depend strongly on the physical properties of the particles such as the particle size, size-distribution (polydispersity) and the saturation magnetization. (C) 2018 Elsevier B.V. All rights reserved.

We report the physicochemical insight into the role of coral-shaped yttrium-iron-garnet (YIG) particles for high electromagnetic interference (EMI) shielding behaviour of YIG-polyaniline (PANI)-Wax composites. We studied the total shielding effectiveness (SET) of various compositions of the composites in X and K-u-band frequencies (8-18 GHz) and came upon with a critical concentration (20 wt% of YIG) for which SET is maximum (-44.8 dB). At this critical concentration, the coral shape of YIG helps in effectively increasing the YIG-PANI interfaces necessary for the multiple scattering of electromagnetic (EM) waves. The scattered microwave is then trapped within the dense coral-network of YIG until they are absorbed therein by PANI via conduction loss; thereby, dramatically enhancing the microwave attenuation. The detailed EMI shielding mechanism is explained based on electrical and magnetic properties of the composites. Our result demonstrates the importance of morphology of the dielectric/magnetic particles and their concentration in the composites for designing an efficient EMI shield.

In this paper we have presented an in-depth study of effect of metallic precursor stacking order on the growth of the Cu 2 ZnSnS 4 (CZTS) thin films. The CZTS films were prepared by employing a two-step process comprising of sequential sputtering of the metal precursors followed by sulfurization. An optimized stacking sequence as well as growth mechanism for obtaining the single phase CZTS has been proposed based on the results of XRD, Raman, XPS, UV–Vis and electrical studies. A combination of Raman analysis and XPS has been carried out to confirm the CZTS phase formation and to detect any minor phases, if present. The occurrence of Raman modes at around 286 and 336 cm −1 for the Zn/Cu/Sn/Cu stack sulfurized at 500 °C indicated the existence of prominent Kesterite CZTS phase. The perfect homogeneous mixing of sequential precursors together with the elemental sulfur was observed in the case of sulfurized stack order of Zn/Cu/Sn/Cu, which yielded single phase CZTS films, and further confirmed by high resolution core level XPS measurements. Stack dependent micro structural features and elemental analysis were also carried out using FESEM attached to EDS. The p-type charge carriers as detected using hot-probe measurement technique and the band-gap energy of ∼1.52 eV as estimated from the absorbance spectrum, suggested that the Zn/Cu/Sn/Cu stack order is most appropriate for realizing single phase CZTS growth using two step method.

High-density polyethylene (HDPE)-based and ultra-high molecular weight polyethylene (UHMWPE)-based composites with carbonaceous reinforcements are being widely investigated for biomedical applications. The enhancement of material properties critically depends on the nature, amount and compatibility of the reinforcement with the polymeric matrix. To this end, this study demonstrates the efficacy of a ‘dual’ hybrid approach of incorporating modified inorganic nanofiller into an optimized polyethylene blend. In particular, a unique synthesis strategy was adopted to design a covalently bonded maleated polyethylene (mPE) grafted modified graphene oxide (mGO) hybrid nanocomposite. In this scheme, polyethyleneimine (PEI) was initially attached onto GO to synthesize amine functionalized GO (GO–PEI). This is followed by mPE grafting, resulting in mGO. Melt-extrusion together with injection moulding of a polymer mix (60% HDPE–40% UHMWPE) with different proportions (less than or equal to 3 wt%) of surface functionalized GO was conducted to develop nanocomposites of different sizes and shapes. When compared with unreinforced PE blend, the nanocomposites with 1 wt% mGO exhibited an increase in ultimate tensile strength by 120% (up to 65 MPa) and elastic modulus by 40% (up to 908 MPa). The uniform dispersion of modified GO nanofillers, confirmed using X-ray micro-computed tomography and transmission electron microscopy, facilitated effective interfacial adhesion and compatibility with the hybrid polymer matrix. The variation in mechanical properties with GO/mGO addition to PE blend was critically discussed in reference to the structural modification of GO, crystallinity and nature of dispersion of fillers. Importantly, the nanocomposites support the attachment and proliferation of C2C12 murine myoblast cells over 3 days in culture in a statistically insignificant manner with respect to polymer blends without any nanofiller. Taken together, the experimental results suggest that HDPE/UHMWPE/mGO is a promising biomaterial for bone tissue engineering applications.

A self-powered, broad band and ultrafast photodetector based on n + -InGaN/AlN/n-Si(111) heterostructure is demonstrated. Si-doped (n + type) InGaN epilayer was grown by plasma-assisted molecular beam epitaxy on a 100 nm thick AlN template on an n-type Si(111) substrate. The n + -InGaN/AlN/n-Si(111) devices exhibit excellent self-powered photoresponse under UV-visible (300-800 nm) light illumination. The maximum response of this self-powered photodetector is observed at 580 nm for low-intensity irradiance (0.1 mW/cm 2 ), owing to the deep donor states present near the InGaN/AlN interface. It shows a responsivity of 9.64 A/W with rise and fall times of 19.9 and 21.4 I¼s, respectively. A relation between the open circuit voltage and the responsivity has been realized.

Robust electrocatalysts toward the resourceful and sustainable generation of hydrogen by splitting of water via electrocatalytic hydrogen evolution reaction (HER) are a prerequisite to realize high-efficiency energy research. Highly electroactive catalysts for hydrogen production with ultralow loading of platinum (Pt) have been under exhaustive exploration to make them cutting-edge and cost-effectively reasonable for water splitting. Herein, we report the synthesis of hierarchically structured nickel pyrophosphate (beta-Ni2P2O7) by a precipitation method and nickel phosphate (Ni-3(PO4)(2)) by two different synthetic routes, namely, simple cost-effective precipitation and solution combustion processes. Thereafter, Pt-decorated nickel pyrophosphate and nickel phosphate (beta-Ni2P2O7/Pt and Ni-3(PO4)(2)/Pt) were prepared by using potassium hexachloroplatinate and ascorbic acid. The fabricated novel nickel pyrophosphate and nickel phosphate/Pt materials were utilized as potential and affordable electrocatalysts for HER by water splitting. The detailed electrochemical studies revealed that the beta-Ni2P2O7/Pt (1 mu g.cm(-2) Pt) electrocatalyst showed excellent electrocatalytic performances for HER in acidic solution with an overpotential of 28 mV at -10 mA.cm(-2), a Tafel slope of 32 mV.dec, and an exchange current density (j(0)) of -1.31 mA.cm(-2), which were close to the values obtained using the Vulcan/Pt (8.0 mu g.cm(-2) Pt), commercial benchmarking electrocatalyst with eight times higher Pt amount. Furthermore, the beta-Ni2P2O7/Pt electrocatalyst maintains an excellent stability for over -0.1 V versus RHE for 12 days, keeping j(0) equal after the stability test (-1.28 mA cm(-2)). Very well-distributed Pt NPs inside the cages on the beta-Ni2P2O7 structure with a crystalline pattern of 0.67 nm distance to the Ni2P2O7/Pt electrocatalyst, helping the Volmer-Tafel mechanism with the Tafel reaction as a major rate-limiting step, help to liberate very fast the Pt sites after HER. The high electrocatalytic performance and remarkable durability showed the beta-Ni2P2O7/Pt material to be a promising cost-effective electrocatalyst for hydrogen production.

Lead lithium titanate (PbLi2Ti6O14) was synthesized by combustion route restricting the annealing at 900 degrees C to just 1 minute. Rietveld analysis confirmed orthorhombic (Cmca) product phase with an average particle size similar to 200 nm and surface area of 2 m(2)/g forming secondary porous particles. From bond valence site energy (BVSE) calculations, 1 D ionic conduction was found along c axis with low activation energy (0.23 eV). AC conductivity analysis revealed a bulk conductivity of 2 x 10(-7) S. cm(-1) at room temperature and 1 x 10(-4) S. cm(-1) at 200 degrees C with a switch from extrinsic 1D to intrinsic 2D mechanism at 150. C. Li + diffusion coefficient was calculated to be in the order of 10(-12) cm(2). s(-1). More than 4 lithium (per f. u.) could be reversibly (de) inserted delivering capacity over 160 mAh/g with good cycling retention over 1000 cycles. With a feasible rapid synthesis, good diffusional and electrochemical behavior especially high rate capability, PbLi2Ti6O14 can act as a safe 1.35 V anode for rechargeable Li-ion batteries. (c) The Author(s) 2018. Published by ECS.

Herein, we report the development of a unique architecture by chemically cross-linking salicylic acid (SA)-based poly(anhydride ester) onto a biodegradable amine-functionalized poly(caprolactone) (PCL), using lactic acid as a spacer. The ester and amide linkages in the SA PCL polymer, synthesized through melt condensation, were confirmed by NMR and FT-IR spectroscopic techniques. The enzymatic and nonenzymatic hydrolytic degradation profile exhibited linear degradation kinetics over an extended time period (>5 weeks). The compatibility and growth of C2C12 myoblast cells were found to be significantly improved on the fast-degrading SA PCL substrates compared to those over neat PCL and amine-functionalized PCL. Further, the decreased red blood cell damage, illustrated by 0.39% hemolysis activity and a minimal number of platelet adhesion on a SA PCL polymeric surface confirmed good hemocompatibility of the as-synthesized polymer. Together with a moderate bactericidal property, the spectrum of properties of this novel polymer can be attributed to the synergistic effect of the presence of chemical moieties of SA and amine groups in PCL. In summary, it is considered that a SA PCL-based cross-linked composite can be utilized as a new biodegradable polymer.

Steady shear response of a magnetorheological fluid (MRF) system containing porous mono-disperse magnetite (Fe3O4) spheres synthesized by solvothermal method is demonstrated. In applied magnetic field the interaction between the spherical particles leads to form strong columnar structures enhancing the yield strength and viscosity of the MRFs. The yield strengths of the MRFs also scale up with the concentration of magnetic particles in the fluid. Considering magnetic dipolar interaction between the particles the magneto-mechanical response of the MRFs is explained. Unlike metallic iron particles, the low-density corrosion resistant soft-ferrimagnetic Fe3O4 spherical particles make our studied MRF system efficient and reliable for shock-mitigation/vibration-isolation applications. (C) 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

It has been reported that defect density in ball-milled graphite lattice increases with the milling time. Guided by this, we hypothesized that the oxygen content of graphene oxide can be substantially enhanced by oxidizing ball-milled graphite and also, the oxygen content would monotonically increase with the milling time as the defect sites would be preferred sites for oxidation. Interestingly, we observed that this correlation was not directly proportional for all milling hours. Even though, the defect density of graphite monotonically increased with milling time, the oxygen content of graphene oxide initially increased and then decreased. This was due to milling time dependent change in the size of the graphite plates and consequent relative abundance of the different oxygen containing functional groups on graphene oxide (GO) produced from the milled graphite.

Magnetically soft nickel-zinc ferrite (Ni0.5Zn0.5Fe2O4) powder with high saturation magnetization was synthesized by solution combustion route using metal nitrates as precursors and glycine as fuel. The particles were found to have irregular morphology. Three different concentrations of magnetorheological fluids (MRFs) were prepared by dispersing 10, 20 and 40 wt% of these particles in thin silicone oil. The behaviours of the MRFs were studied under steady shear conditions at different applied magnetic field strengths (B). The yield strength (tau(Y)) and viscosity (eta) of all the MRFs were found to increase with B and particle fill fraction phi, while the response of the MRFs was strongly influenced by the morphology, microstructure and saturation magnetization of the particles. Owing to the low density of the particles, the observed off-state viscosity is high. However, the excellent thermo-oxidative and chemical stabilities of these magnetic oxide particles than metallic magnetic particles make these MRFs dependable for applications in harsh working environments. In addition, the low cost and feasibility of large scale preparation of these magnetic oxides make these MRFs further attractive for industrial applications. (C) 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

We report the magnetic field and particle-concentration dependent steady-state shear-responses of rod shaped Li-Zn ferrite particle based magnetorheological fluids (MRFs). Rod-shaped soft ferrimagnetic Li-Zn ferrite (Li0.4Zn0.2Fe2.4O4) particles were synthesized using the combustion synthesis method. MRFs of three different particle-concentrations (phi = 0.1, 0.2 and 0.4, in weight fraction) were prepared using silicone oil. Their yield strength and dynamic viscosity were studied at different applied magnetic fields (B). With an increase in B and phi, the yield strength ((Y)) of the MRFs increases. This behaviour is assigned to the formation of stronger columnar structures of the magnetically interacting particles which resist the flow (shear) of the MRF. For the MRF with phi = 0.4 and B = 1.2 T, we observed a maximum (Y) value of approximate to 1.25 kPa. Furthermore, we observed that, based on the on-state to off-state viscosity ratio ((on)/(off)) at a particular operating B value, the optimum particle concentration required for energy- and cost-efficient operation of the MRFs can be chosen. The absence of a stabilizing-agent or de-agglomerating-coating, the low density, and the excellent oxidation- and corrosion-resistance of the soft ferrimagnetic rod-shaped Li-Zn ferrite particles make this MRF-system highly versatile and economical for many magneto-mechanical applications.

Nonpolar a-plane GaN epitaxial films were grown on an r-plane sapphire using the plasma-assisted molecular beam epitaxy system, with various nitrogen plasma power conditions. The crystallinity of the films was characterized by high-resolution Xray diffraction and reciprocal space mapping. Using the X-ray ``rocking curve-phi scan'', 0002],1-100], and 1-102] azimuth angles were identified, and interdigitated electrodes along these directions were fabricated to evaluate the direction-dependent UV photoresponses. UV responsivity (R) and internal gain (G) were found to be dependent on the azimuth angle and in the order of 0002] > 1-102] > 1-100], which has been attributed to the enhanced crystallinity and lowest defect density along 0002] azimuth. The temporal response was very stable irrespective of growth conditions and azimuth angles. Importantly, response time, responsivity, and internal gain were 210 ms, 1.88 A W-1, and 648.9%, respectively, even at a bias as low as 1 V. The results were validated using the Silvaco Atlas device simulator, and experimental observations were consistent with simulated results. Overall, the photoresponse is dependent on azimuth angles and requires further optimization, especially for materials with in-plane crystal anisotropy.

EMI shielding properties of nanocomposite containing lead hexaferrite (PFO) and polyaniline (PANI), a conducting polymer, was studied in X and K-u band frequencies. The nanocomposite shows enhanced EMI shielding properties than that of the pure PANI. Incorporation of PFO particles in the PANI enhances the total shielding effectiveness (SET) up to -24 dB at 18 GHz. This means that these nanocomposites can shield similar to 99% of the incoming EM radiation. The PFO/PANI shows much higher attenuation constant values over the measured frequency range. By adding the PFO in the PANI we have created more interfaces between Wax-PFO,Wax-PANI, PANI-PFO and PFO-PANI. These enhanced interfaces lead to Maxwell-Wagner polarization which results in a higher dielectric loss than only PANI.

An efficient buffer layer scheme has been designed to address the issue of curvature management during metalorganic chemical vapour deposition growth of GaN on Si (111) substrate. This is necessary to prevent cracking of the grown layer during post-growth cooling down from growth temperature to room temperature and to achieve an allowable bow (

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X-ray diffraction, thermo gravimetric, scanning electron microscopy, and Impedance analyzer for their structural, morphology, and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization/MWS effect. Theoretical models were employed to rationalize the dielectric behavior of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both beta and alpha relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization. POLYM. ENG. SCI., 54:551-558, 2014. (c) 2013 Society of Plastics Engineers

The thermal transitions in the copolymer of 1,6-hexanediol diacrylate (HDDA) and methyl methacrylate (MMA) was investigated to understand its use in microstereolithography. The glass transition temperature and the effect of interaction on this transition process was investigated by means of temperature modulated differential scanning calorimetry (TMDSC). The heat capacities were determined and PHDDA rich phases showed lower heat capacity than PMMA rich phases. The frequency dependence of glass transitions were studied by varying the modulation period of TMDSC and confirmed by dielectric relaxation spectroscopy. Vogel Fulcher Tammann Hesse (VFTH) parameters of homo and copolymers have also been reported.

A new family of ricinoleic acid based polyesters was synthesized using catalyst free melt-condensation polymerization with sebacic acid, citric acid, mannitol and ricinoleic acid as precursors. The use of FT-IR and NMR characterisation techniques confirms the presence of ester linkages in the as-synthesized polymers. Depending on the precursor combination, their relative amount and the degree of curing, a broad range of elastic modulus (22-327 MPa) and tensile strength (0.7-12.7 MPa) can be obtained in the newly synthesized biopolymers. The polymers show rubbery behaviour at a physiological temperature (37 degrees C) and the contact angles of the synthesized polymers fall in the range of 42 degrees to 71 degrees, making them ideal substrates to study delivery of drugs through polymer scaffolds. The cytocompatibility assessment of the cured polymers confirmed good cell attachment and growth of smooth muscle cells (C2C12 myoblast cells). Importantly, oriented cell growth was observed after culturing myoblast cells for 3 days. The in vitro degradation in PBS indicates that the mild cured polymers follow a first order reaction kinetics and have degradation rate constants in the range of 0.009-0.038 h(-1), depending on the relative proportions of monomers. Overall, the results of our study indicate that the physical properties can be tailored by varying the composition of the monomers and curing conditions in the newly developed polyesters. Hence, they may be used as potential substrates for tissue engineering scaffolds and for localized drug delivery.

In this letter we present systematic studies of the dynamics of surface adsorption of various chemicals on ultra-thin single crystalline gold nanowires (AuNW) through sensitive resistance fluctuation spectroscopy measurements coupled with ab initio simulations. We show that, contrary to expectations, the adsorption of common chemicals like methanol and acetone has a profound impact on the electrical transport properties of the AuNW. Our measurements and subsequent calculations establish conclusively that in AuNW, semiconductor-like sensitivity to the ambient arises because of changes induced in its local density of states by the surface adsorbed molecules. The extreme sensitivity of the resistance fluctuations of the AuNW to ambient suggests their possible use as solid-state sensors. Published by AIP Publishing.

Polycrystalline BiFeO and BiGdFeTi (x) O (3) (x = 0, 0.01, 0.05 and 0.1) samples were synthesized by solid-state reaction route. Structural, magnetic and ferroelectric properties of these samples were investigated. X-ray powder diffraction (XRD) results confirmed the presence of a significant amount of BiFe impurity phase in the undoped BiFeO sample. Mossbauer spectroscopy studies corroborated the XRD studies to confirm the presence of impurity phase. We have observed that gadolinium (Gd) and titanium (Ti) doping, respectively, on Bi and Fe sites facilitated a significant reduction in the impurity phase formation in BiFeO. Interestingly, Gd-doping significantly reduced the impurity phase formation as compared to the undoped BiFeO sample. This impurity phase formation was further overcome by doping higher (x 0.05) amounts of Ti in BiFeO. The crystallographic site occupancies of Gd and Ti were confirmed by Rietveld refinement of XRD data, Mossbauer spectroscopy and magnetization measurements. An enhancement in ferromagnetic properties along with moderate ferroelectric properties have been observed after co-doping. There was an increasing trend in remnant polarization (P ) with the increase in Ti concentration besides an improvement in the characteristic saturation magnetization. Our results demonstrate that Gd and Ti doping could be used to enhance multifunctional properties of BiFeO ceramics to enable them as potential material for various devices.

The gamma-phase poly (vinylidene fluoride) (PVDF) films are usually prepared using dimethyl sulfoxide (DMSO) solvent, regardless of preparation temperature. Here we report the crystallization of both alpha and gamma-phase PVDF films by varying preparation temperature using DMSO solvent. The gamma-phase PVDF films were annealed at 70, 90, 110, 130 and 160 degrees C for five hours. The changes in the phase contents in the PVDF at different annealing conditions have been described. When thin films were annealed at 90 degrees C for 5 h, maximum percentage of beta-phase appears in PVDF thin films. The gamma-phase PVDF films completely converted to alpha-phase when they were annealed at 160 degrees C for 5 h. From X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC) and Raman studies, it is confirmed that the PVDF thin films, cast from solution and annealed at 90 degrees C for 5 h, have maximum percentage of beta-phase. The beta-phase PVDF shows a remnant polarization of 4.9 mu C/cm(2) at 1400 kV/cm at 1 Hz.

We report the synthesis of aligned arrays of millimeter long carbon nanotubes (CNTs), from benzene and ferrocene as the molecular precursor and catalyst respectively, by a one-step chemical vapor deposition technique. The length of the grown CNTs depends on the reaction temperature and increases from similar to 85 mu m to similar to 1.4 mm when the synthesis temperature is raised from 650 to 1100 degrees C, while the tube diameter is almost independent of the preparation temperature and is similar to 80 nm. The parallel arrangement of the CNTs, as well as their tube diameter can be verified spectroscopically by small angle X-ray scattering (SAXS) studies. Based on electron diffraction scattering (EDS) studies of the top and the base of the CNT films, a root growth process can be deduced.

Graphene oxide-intercalated alpha-metal hydroxides were prepared using layers from the delaminated colloidal dispersions of cetyltrimethylammonium-intercalated graphene oxide and dodecylsulfate-intercalated alpha-hydroxide of nickel/cobalt as precursors. The reaction of the two dispersions leads to de-intercalation of the interlayer ions from both the layered solids and the intercalation of the negatively charged graphene oxide sheets between the positively charged layers of the alpha-hydroxide. Thermal decomposition of the intercalated solids yields graphene/nanocrystalline metal oxide composites. Electron microscopy analysis of the composites indicates that the nanoparticles are intercalated between graphene layers. (C) 2010 Elsevier Ltd. All rights reserved.

The flow properties of carbonyl iron (CI) and electrolytic iron (EI) micro-particles based magnetorheological fluids (MRFs) were studied under steady shear conditions at different applied magnetic field strengths (B). The CI particles were spherically-shaped having a wide size distribution ranging from similar to 0.2 to similar to 3 mu m whereas the EI particles were irregularly-shaped with much bigger particles of sizes between similar to 20 mu m and 80 mu m. To prepare the MRFs, 40 wt% each of CI and EI micro-particles were separately dispersed in silicone oil. In the MRFs the particles do not contain any surfactant/coating and the MRFs do not include any stabilizers in them. According to the magnetorheological results, although the yield strength (tau(Y)) and viscosity (eta) of both MRFs increase with increase in B, there is deviation from the parallelism in increase of tau(Y) and eta with B. This suggests that tau(Y) and eta depend strongly on the physical parameters of Fe-particles such as the shape, size and saturation magnetization. The effect of saturation magnetization on steady state shear response of the MRFs dominates over the effect of shape and size of the particles.

We report stable ultrathin Au nanowires supported on reduced graphene oxide with outstanding electrocatalytic activity for borohydride oxidation., We report stable ultrathin Au nanowires supported on reduced graphene oxide with outstanding electrocatalytic activity for borohydride oxidation. Electrochemical impedance spectroscopy measurements showed abnormal inductive behavior, indicative of surface reactivation. DFT calculations indicate that the origin of the high activity stems from the position of the Au d-band center.

There has been a continuous surge toward developing new biopolymers that exhibit better in vivo biocompatibility properties in terms of demonstrating a reduced foreign body response (FBR). One approach to mitigate the undesired FBR is to develop an implant capable of releasing anti-inflammatory molecules in a sustained manner over a long time period. Implants causing inflammation are also more susceptible to infection. In this article, the in vivo biocompatibility of a novel, biodegradable salicylic acid releasing polyester (SAP) has been investigated by subcutaneous implantation in a mouse model. The tissue response to SAP was compared with that of a widely used biodegradable polymer, poly(lactic acid-co-glycolic acid) (PLGA), as a control over three time points: 2, 4, and 16 weeks postimplantation. A long-term in vitro study illustrates a continuous, linear (zero order) release of salicylic acid with a cumulative mass percent release rate of 7.34 x 10(-4) h(-1) over similar to 1.5-17 months. On the basis of physicochemical analysis, surface erosion for SAP and bulk erosion for PLGA have been confirmed as their dominant degradation modes in vivo. On the basis of the histomorphometrical analysis of inflammatory cell densities and collagen distribution as well as quantification of proinflammatory cytokine levels (TNF-alpha and IL-1 beta), a reduced foreign body response toward SAP with respect to that generated by PLGA has been unambiguously established. The favorable in vivo tissue response to SAP, as manifest from the uniform and well-vascularized encapsulation around the implant, is consistent with the decrease in inflammatory cell density and increase in angiogenesis with time. The above observations, together with the demonstration of long-term and sustained release of salicylic acid, establish the potential use of SAP for applications in improved matrices for tissue engineering and chronic wound healing.

Multiwalled carbon nanotubes have been prepared by pyrolysing tetrahydrofuran (THF) in the presence of nickelocene. Pyrolysis of the precursor mixture has been achieved at temperature as low as 600 degrees C. In this simple approach no carrier gas has been used. The yield of purified carbon nanotubes is found to be more than 65%. Characterization of the as-prepared and purified nanotubes are done by Xray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectra.

Thin films of a hydrated phase of tungsten oxide, viz. hydrotungstite,have been prepared on glass substrates by dip-coating method using ammonium tungstate precursor solution. X-ray diffraction shows the films to have a strong b-axis orientation. The resistance of the films is observed to be sensitive to the humidity content of the ambient,indicating possible applications of these films for humidity sensing. Ahome made apparatus designed to measure the d.c. electrical resistance in response to exposure to controlled pulses of a sensing gas has been employed to evaluate the sensitivity of the hydrotungstite films towards humidity.

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C2 H2 , B powder, and NH3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings.

Although ultrathin Au nanowires (similar to 2 nm diameter) are expected to demonstrate several interesting properties, their extreme fragility has hampered their use in potential applications. One way to improve the stability is to grow them on substrates; however, there is no general method to grow these wires over large areas. The existing methods suffer from poor coverage and associated formation of larger nanoparticles on the substrate. Herein, we demonstrate a room temperature method for growth of these nanowires with high coverage over large areas by in situ functionalization of the substrate. Using control experiments, we demonstrate that an in situ functionalization of the substrate is the key step in controlling the areal density of the wires on the substrate. We show that this strategy works for a variety of substrates ranging like graphene, borosil glass, Kapton, and oxide supports. We present initial results on catalysis using the wires grown on alumina and silica beads and also extend the method to lithography-free device fabrication. This method is general and may be extended to grow ultrathin Au nanowires on a variety of substrates for other applications.

A correlation between gas sensing properties and defect induced Room Temperature Ferromagnetism (RTFM) is demonstrated in non-stoichiometric SnO2 prepared by solution combustion method. The presence of oxygen vacancies (V-O), confirmed by RTFM is identified as the primary factor for enhanced gas sensing effect. The as-prepared SnO2 shows high saturation magnetization of similar to 0.018 emu/g as compared to similar to 0.002 and similar to 0.0005 emu/g in annealed samples and SnO2 prepared by precipitation respectively. The SnO2 prepared by precipitation which is an equilibrium method of synthesis shows lesser defects compared to the combustion product and hence exhibits lesser sensitivity in spite of smaller crystallite size. The study utilizes RTFM as a potential tool to characterize metal oxide gas sensors and recognizes the significance of oxygen vacancies in sensing mechanism over the microstructure. (C) 2014 AIP Publishing LLC.

In order to suppress chronic inflammation while supporting cell proliferation, there has been a continuous surge toward development of polymers with the intention of delivering anti-inflammatory molecules in a sustained manner. In the above backdrop, we report the synthesis of a novel, stable, cross-linked polyester with salicylic acid (SA) incorporated in the polymeric backbone and propose a simple synthesis route by melt condensation. The as-synthesized polymer was hydrophobic with a glass transition temperature of 1 degrees C, which increases to 17 degrees C upon curing. The combination of NMR and FT-IR spectral techniques established the ester linkages in the as-synthesized SA-based polyester. The pH-dependent degradation rate and the rate of release of salicylic acid from the as-synthesized SA-based polymer were studied at physiological conditions in vitro. The polyester underwent surface erosion and exhibited linear degradation kinetics in which a change in degradation rate is observed after 4-10 days and 24% mass loss was recorded after 4 months at 37 degrees C and pH 7.4. The delivery of salicylic acid also showed a similar change in slopes, with a sustained release rate of 3.5% in 4 months. The cytocompatibility studies of these polyesters were carried out with C2C12 murine myoblast cells using techniques like MTT assay and flow cytometry. Our results strongly suggest that SA-based polyester supports cell proliferation for 3 days in culture and do not cause cell death (

Oxidation of small organic molecules in a fuel cell is a viable method for energy production. However, the key issue is the development of suitable catalysts that exhibit high efficiencies and remain stable during operation. Here, we demonstrate that amine-modified ZnO nanorods on which ultrathin Au nanowires are grown act as an excellent catalyst for the oxidation of ethanol. We show that the modification of the ZnO nanorods with oleylamine not only modifies the electronic structure favorably but also serves to anchor the Au nanowires on the nanorods. The adsorption of OH(-) species on the Au nanowires that is essential for ethanol oxidation is facilitated at much lower potentials as compared to bare Au nanowires leading to high activity. While ZnO shows negligible electrocatalytic activity under normal conditions, there is significant enhancement in the activity under light irradiation. We demonstrate a synergistic enhancement in the photoelectrocatalytic activity of the ZnO/Au nanowire hybrid and provide mechanistic explanation for this enhancement based on both electronic as well as geometric effects. The principles developed are applicable for tuning the properties of other metal/semiconductor hybrids with potentially interesting applications beyond the fuel cell application demonstrated here.

The tie-lines delineating intercrystalline ion-exchange equilibria between MgAl2O4-MgCr2O4 spinel solid solution and Al2O3-CP2O3 solid solution with corundum structure have been determined at 1473 K by electron microprobe and X-ray diffraction (XRD) analysis of equilibrated phases. The tie-lines are skewed to the solid solution 0.7MgAl(2)O(4)-0.3MgCr(2)O(4). The lattice parameters and molar volumes of both the solid solution series exhibit positive deviations from Vegard's and Retger's laws, respectively. Activities in the spinel solid solution are derived from the tie-line information and thermodynamic data on Al2O3-Cr2O3 solid solution available in the literature. Activities of Mg0.5CrO2 and Mg0.5AlO2 in the spinel solid solution exhibit strong positive deviations from Raoult's law over most of the composition range, However, activity of Mg0.5CrO2 exhibits mild negative deviation for compositions rich in Mg0.5CrO2. The activity-composition relationship in the spinel solid solution is analyzed in terms of the intracrystalline exchange of cations between the tetrahedral and octahedral sites of the spinel structure. The intracrystalline ion exchange is governed by site preference energies of the cations, The difference between the Gibbs energy of mixing calculated using the cation mixing model and the experimental data is taken as a measure of the strain contribution arising from the difference in the radii of Al3+ and Cr3+ ions. The large positive strain enthalpy suggests the onset of immiscibility in the spinel solid solution at low temperatures. The computed critical temperature and composition for phase separation are 802 (+/-20) K and X-MgCr2O4 = 0.46 (+/-0.02), respectively

Recent experimental investigations of phase equilibria and thermodynamic properties of the systems M-Pb-O, where M = Ca, Sr or Ba, indicate a regular increase in thermodynamic stability of ternary oxides, MPbO3 and M2PbO4, with increasing basicity of the oxide of the alkaline-earth metal. Number of stable interoxide compounds at 1100 K in the systems M-Pb-O (M = Mg, Ca, Sr, Ba) increases in unit increments from Mg to Ba. In this paper, experimentally determined standard Gibbs energies of formation of M2PbO4 (M = Ca, Sr, Ba) and MPbO3 (M = Sr, Ba) from their component binary monoxides and oxygen gas are combined with an estimated value for CaPbO3 to delineate systematic trends in thermodynamic stability of the ternary oxides. The trends are interpreted using concepts of tolerance factor and acid-base interactions. All the ternary oxides in these systems contain lead in the tetravalent state. The small Pb4+ ions polarize the surrounding oxygen ions and cause the formation of oxyanions which are acidic in character. Hence, the higher oxidation state of lead is stabilized in the presence of basic oxides of alkaline-earth group. A schematic subsolidus temperature-composition phase diagram is presented for the system BaO-PbO-O-2 to illustrate the change in oxidation states in binary and ternary oxides with temperature.

Nanocrystalline powders of ferroelectric bismuth vanadate, Bi4V2O11 (n-BiV), with crystallite size less than 50 nm, were obtained by mechanical milling of a stoichiometric mixture of bismuth oxide and vanadium pentoxide. The n-BiV powders on sintering yielded high-density, fine-grained ceramics with improved dielectric and polar characteristics. Dielectric studies on samples obtained from milled powders indicated that the ferroelectric-to-paraelectric phase transition temperature is strongly frequency dependent. The Curie–Weiss law is found to be valid only at a temperature away from the transition temperature, confirming the diffused nature of the transition, which is attributed to the presence of compositional inhomogeneity, because of partial reduction of vanadium.

For the purpose of water purification, novel and low-cost adsorbents which are promising replacements for activated carbon are being actively pursued. However, a single-phase material that adsorbs both cationic and anionic species remains elusive. Hence, a low-cost, multiphase adsorbent bed that purifies water containing both anionic and cationic pollutants is a desirable alternative. We choose anionic (Congo red, Orange G) and cationic (methylene blue, malachite green) dyes as model pollutants. These dyes are chosen since they are widely found in effluents from textile, leather, fishery, and pharmaceutical industries, and their carcinogenic, mutagenic, genotoxic, and cytotoxic impact on mammalian cells is well-established. We show that ZnO, (Zn0.24Cu0.76)O and cobalt ferrite based multiphase fixed adsorbent bed efficiently adsorbs model anionic (Congo red, Orange G) and cationic (methylene blue and malachite green) pollutants, and their complex mixtures. All adsorbent phases are synthesized using room-temperature, high-yield (similar to 96-100%), green chemical processes. The nanoadsorbents are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and zeta potential measurements. The constituent nanophases are deliberately chosen to be beyond 50 nm, in order to avoid the nanotoxic size regime of oxides. Adsorption characteristics of each of the phases are examined. Isotherm based analysis shows that adsorption is both spontaneous and highly favorable. zeta potential measurements indicate that electrostatic interactions are the primary driving force for the observed adsorption behavior. The isotherms obtained are best described using a composite Langmuir-Freundlich model. Pseudo-first-order, rapid kinetics is observed (with adsorption rate constants as high as 0.1-0.2 min(-1) in some cases). Film diffusion is shown to be the primary mechanism of adsorption.

Glasses of the alkali tin phosphate system have been investigated. The infrared absorption and fluorescence spectra of the glasses have been examined. It is found that tin is present in both + 2 and + 4 oxidation states. Also tin ions occupy four- or six-coordinated sites in the glass.

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

The effect of oxygen pressure (P-O2) on the Yttrium Iron Garnet (YIG) thin films were grown on silicon substrate by rf sputtering method was studied. The as-deposited films at 300K were amorphous in nature. The crystallization of these films was achieved by annealing at a temperature of 800 degrees C/1hr in air. The structural, microstructural and magnetic properties were found to be dependent on P-O2.

InN quantum dots (QDs) were fabricated on silicon nitride/Si (111) substrate by droplet epitaxy. Single-crystalline structure of InN QDs was verified by transmission electron microscopy, and the chemical bonding configurations of InN QDs were examined by x-ray photoelectron spectroscopy. Photoluminescence measurement shows a slight blue shift compared to the bulk InN, arising from size dependent quantum confinement effect. The interdigitated electrode pattern was created and current-voltage (I-V) characteristics of InN QDs were studied in a metal-semiconductor-metal configuration in the temperature range of 80-300K. The I-V characteristics of lateral grown InN QDs were explained by using the trap model. (C) 2011 American Institute of Physics. [doi:10.1063/1.3651762]

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

We demonstrate an ultrafast method for the formation of, graphene supported Pt catalysts by the co-reduction of graphene oxide and Pt salt using ethylene glycol under microwave irradiation conditions. Detailed analysis of the mechanism of formation of the hybrids indicates a synergistic co-reduction mechanism whereby the presence of the Pt ions leads to a faster reduction of GO and the presence of the defect sites on the reduced GO serves as anchor points for the heterogeneous nucleation of Pt. The resulting hybrid consists of ultrafine nanoparticles of Pt uniformly distributed on the reduced GO susbtrate. We have shown that the hybrid exhibits good catalytic activity for methanol oxidation and hydrogen conversion reactions. The mechanism is general and applicable for the synthesis of other multifunctional hybrids based on graphene.

Ce1-xSnxO2 (x = 0.1-0.5) solid solution and its Pd substituted analogue have been prepared by a single step solution combustion method using tin oxalate precursor. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H-2/temperature programmed redution (TPR) studies. The cubic fluorite structure remained intact up to 50% of Sri substitution in CeO2, and the compounds were stable up to 700 C. Oxygen storage capacity of Ce1-xSnxO2 was found to be much higher than that of Ce1-xZrxO2 due to accessible Ce4+/Ce3+ and Sn4+/Sn2+ redox couples at temperatures between 200 and 400 C. Pd 21 ions in Ce0.78Sn0.2Pd0.02O2-delta are highly ionic, and the lattice oxygen of this catalyst is highly labile, leading to low temperature CO to CO2 conversion. The rate of CO oxidation was 2 mu mol g(-1) s(-1) at 50 degrees C. NO reduction by CO with 70% N-2 selectivity was observed at similar to 200 degrees C and 100% N-2 selectivity below 260 degrees C with 1000-5000 ppm NO. Thus, Pd2+ ion substituted Ce1-xSnxO2 is a superior catalyst compared to Pd2+ ions in CeO2, Ce1-xZrxO2, and Ce1-xTixO2 for low temperature exhaust applications due to the involvement of the Sn2+/Sn4+ redox couple along with Pd2+/Pd-0 and Ce4+/Ce3+ couples.

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P2O 7 4− ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities.

A new pyrolysis technique has been developed for the synthesis of multi-walled carbon nanotubes (MWCNTs). In this simple method diethyl ether and nickelocene is pyrolysized in a reaction quartz tube without using carrier gas. The samples are prepared at pyrolysis temperatures of 650 and 950 ∘ C and the effect of temperature on the tube morphology investigated. Purification has been done following the standard oxidation and acid bath treatment. The as-synthesized and purified nanotubes have been characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and micro-Raman spectroscopy. The technique has great advantages such as low cost and easy operation for the production of CNTs.