Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Evaluation of DNA binding, antioxidant and cytotoxic activity of mononuclear Co(III) complexes of 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde thiosemicarbazones

Four new 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde N-substituted thiosemicarbazone ligands (H-2-LR, where R = H, Me, Et or Ph) and their corresponding new cobalt(III) complexes have been synthesized and characterized. The structures of the complexes 2 and 3 were determined by single crystal X-ray diffraction analysis. The interactions of the new complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Antioxidant studies of the new complexes showed that the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of complexes 1-4 against A549 cell line was assayed which showed higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations. (C) 2012 Elsevier Masson SAS. All rights reserved.

Effect of Grain Size on Structural and Magnetic Properties of CuFe2O4 Nanograins Synthesized by Chemical Co-Precipitation

CuFe2O4 nanograins have been prepared by the chemical co-precipitation technique and calcined in the temperature range of 200-1200 degrees C for 3 h. A wide range of grain sizes has been observed in this sintering temperature range, which has been determined to be 4 to 56 nm. Formation of ferrite has also been confirmed by FTIR measurement through the presence of wide band near 600 and 430 cm(-1) for the samples in the as-dried condition. Systematic variation of wave number has been observed with the variation of the calcination temperature. B-H loops exhibit transition from superparamagnetic to ferrimagnetic state above the calcination temperature of 900 degrees C. Coercivity of the samples at lower calcination temperature of 900 degrees C reduces significantly and tends towards zero coercivity, which is suggestive of superparamagnetic transition for the samples sintered below this temperature. Frequency spectrum of the real and imaginary part of complex initial permeability have been measured for the samples calcined at different temperature, which shows wide range of frequency stability. Curie temperature, T-c has been measured from temperature dependence initial permeability at a fixed frequency of 100 kHz. Although there is small variation of T-c with sintering temperature, the reduction of permeability with temperature drastically reduce for lower sintering temperature, which is in conformity with the change of B-H loops with the variation of sintering temperatures.

Combining adiabatic and Hartmann-Hahn cross-polarization for sensitivity enhancement in solid state separated local field 2D-NMR experiments of partially ordered systems

In this Letter, we examine magnetization in double- and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and describe their role in determining the sensitivity of a class of separated local field NMR experiments based on Hartmann-Hahn cross-polarization. We observe that for the liquid crystal system studied, a large dilute spin-polarization, obtained initially by the use of adiabatic cross-polarization, can enhance the sensitivity of the above experiment. The signal enhancement factors, however, are found to vary and depend on the local dynamics. The experimental results have been utilized to obtain the local order-parameters of the system. (C) 2012 Elsevier B. V. All rights reserved.

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd2O3:Eu3+ (4 mol%) co-doped with Bi3+ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800A degrees C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV-Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer's method and Williamson-Hall plots and are found to be in the ranges 40-60 nm and 30-80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at similar to 590, 612 and 625 nm, which are due to the transitions D-5(0)-> F-7(0), D-5(0)-> F-7(2) and D-5(0)-> F-7(3) of Eu3+, respectively. It is observed that a significant quenching of Eu3+ emission was observed under 230 nm excitation when Bi3+ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu3+ ions was enhanced by incorporation of Bi3+ (5 mol%) ions. The introduction of Bi3+ ions broadened the excitation band of Eu3+ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s(2)-> 6s6p transition of Bi3+ ions, implying a very efficient energy transfer from Bi3+ ions to Eu3+ ions. The gamma radiation response of Gd2O3:Eu3+ exhibited a dosimetrically useful glow peak at 380A degrees C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd2O3:Eu3+, Bi3+ phosphors have promising applications in solid-state lighting.

Sliding wear behavior of plasma nitrided Austenitic Stainless Steel Type AISI 316LN in the temperature range from 25 to 400 degrees C at 10(-4) bar

There is a research knowledge gap for the dry wear data of nitride treated Stainless Steel in high temperature and high vacuum environment. In order to fill this gap, plasma nitriding was done on austenitic Stainless Steel type AISI 316LN (316LN SS) and dry sliding wear tests have been conducted at 25 degrees C, 200 degrees C and 400 degrees C in high vacuum of 1.6 x 10(-4) bar. The two different slider material (316LN SS and Colmonoy) and two different sliding speeds (0.0576 m/s and 0.167 m/s) have been used. The tribological parameters such as friction coefficient, wear mechanism and volume of metal loss have been evaluated. Scanning Electron Microscopy (SEM) was used to study the surface morphology of the worn pins and rings. Electronic balancing machine was used to record the mass of metal loss during wear tests. The 2D optical profilometer was used to measure the depth of the wear track. The Plasma Nitride treated 316LN SS rings (PN rings) exhibit excellent wear resistance against 316LN SS pin and Colmonoy pin at all temperatures. However, PN ring vs. Colmonoy pin Pair shows better wear resistance than PN ring vs. 316LN SS pin Pair at higher temperature. (C) 2012 Elsevier B.V. All rights reserved.

Enhancing the magnetic characteristics of BiFeO3 nanoparticles by Ca, Ba co-doping

Multiferroic nanoparticles (NPs) of pristine and Ca, Ba co-doped BiFeO3 were synthesized by a facile sal gel route. Co-doping was done by fixing the total dopant concentration at 5 mol% and then the relative concentrations of Ca and Ba was varied. Structural, optical and magnetic properties of the NPs were investigated using different techniques. UV-Vis absorption spectra of BiFeO3 NPs showed a substantial blue shift of similar to 100 nm (530 nm -> 430 nm) on Ca. Ba co-doping which corresponds to increase in band gap by 0.5 eV. Fe-57 Mossbauer spectroscopy confirmed that iron is present only in 3(+) valence state in all co-doped samples. The coercive field increased by 18 times for Bi0.95Ca0.01Ba0.04FeO3 samples, which is the maximum enhancement, observed amongst all the 5 mol% doped samples. At the equimolar (2.5 mol % each) concentration of co-dopants, the coercive field shows a significant enhancement of about 9 times (220 Oe -> 2014 Oe) with concomitant increase in saturation magnetization by 7 times. Thus, equimolar co-doping causes simultaneous enhancement of the twin aspects of magnetic properties thereby making them better suited for device applications. (C) 2012 Elsevier B.V. All rights reserved.

Vaporization and collision modeling of liquid fuel sprays in a co-axial fuel and air pre-mixer

Droplet collision occurs frequently in regions where the droplet number density is high. Even for Lean Premixed and Pre-vaporized (LPP) liquid sprays, the collision effects can be very high on the droplet size distributions, which will in turn affect the droplet vaporization process. Hence, in conjunction with vaporization modeling, collision modeling for such spray systems is also essential. The standard O'Rourke's collision model, usually implemented in CFD codes, tends to generate unphysical numerical artifact when simulations are performed on Cartesian grid and the results are not grid independent. Thus, a new collision modeling approach based on no-time-counter method (NTC) proposed by Schmidt and Rutland is implemented to replace O'Rourke's collision algorithm to solve a spray injection problem in a cylindrical coflow premixer. The so called ``four-leaf clover'' numerical artifacts are eliminated by the new collision algorithm and results from a diesel spray show very good grid independence. Next, the dispersion and vaporization processes for liquid fuel sprays are simulated in a coflow premixer. Two liquid fuels under investigation are jet-A and Rapeseed Methyl Esters (RME). Results show very good grid independence in terms of SMD distribution, droplet number distribution and fuel vapor mass flow rate. A baseline test is first established with a spray cone angle of 90 degrees and injection velocity of 3 m/s and jet-A achieves much better vaporization performance than RME due to its higher vapor pressure. To improve the vaporization performance for both fuels, a series of simulations have been done at several different combinations of spray cone angle and injection velocity. At relatively low spray cone angle and injection velocity, the collision effect on the average droplet size and the vaporization performance are very high due to relatively high coalescence rate induced by droplet collisions. Thus, at higher spray cone angle and injection velocity, the results expectedly show improvement in fuel vaporization performance since smaller droplet has a higher vaporization rate. The vaporization performance and the level of homogeneity of fuel-air mixture can be significantly improved when the dispersion level is high, which can be achieved by increasing the spray cone angle and injection velocity. (C) 2012 Elsevier Ltd. All rights reserved.

Completely random nanoporous Cu4O3-CuO-C composite thin films for potential application as multiple channel photonic band gap based filter in the telecommunication wavelengths

In 2003, Babin et al. theoretically predicted (J. Appl. Phys. 94:4244, 2003) that fabrication of organic-inorganic hybrid materials would probably be required to implement structures with multiple photonic band gaps. In tune with their prediction, we report synthesis of such an inorganic-organic nanocomposite, comprising Cu4O3-CuO-C thin films that experimentally exhibit the highest (of any known material) number (as many as eleven) of photonic band gaps in the near infrared. On contrary to the report by Wang et al. (Appl. Phys. Lett. 84:1629, 2004) that photonic crystals with multiple stop gaps require highly correlated structural arrangement such as multilayers of variable thicknesses, we demonstrate experimental realization of multiple stop gaps in completely randomized structures comprising inorganic oxide nanocrystals (Cu4O3 and CuO) randomly embedded in a randomly porous carbonaceous matrix. We report one step synthesis of such nanostructured films through the metalorganic chemical vapor deposition technique using a single source metalorganic precursor, Cu-4(deaH)(dea)(oAc)(5) a <...aEuro parts per thousand(CH3)(2)CO. The films displaying multiple (4/9/11) photonic band gaps with equal transmission losses in the infrared are promising materials to find applications as multiple channel photonic band gap based filter for WDM technology.

A new diketopyrrolopyrrole-based co-polymer for ambipolar field-effect transistors and solar cells

A new thieno3,2-b]thiophenediketopyrrolopyrrole-benzo1,2-b:4,5-b']dithio phene based narrow optical gap co-polymer (PTTDPP-BDT) has been synthesized and characterized for field-effect transistors and solar cells. In field-effect transistors the polymer exhibited ambipolar charge transport behaviour with maximum hole and electron mobilities of 10(-3) cm(2) V-1 s(-1) and 10(-5) cm(2)V(-1) s(-1), respectively. The respectable charge transporting properties of the polymer were consistent with X-ray diffraction measurements that showed close molecular packing in the solid state. The difference in hole and electron mobilities was explained by density functional theory calculations, which showed that the highest occupied molecular orbital was delocalized along the polymer backbone with the lowest unoccupied molecular orbital localized on the bis(thieno3,2-b]thiophene)diketopyrrolopyrrole units. Bulk heterojunction photovoltaic devices with the fullerene acceptor PC70BM were fabricated and delivered a maximum conversion efficiency of 3.3% under AM1.5G illumination. (C) 2012 Elsevier B.V. All rights reserved.

Preferential oxidation of CO on Ni/CeO2 catalysts in the presence of excess H-2 and CO2

Preferential oxidation of CO (CO-PROX) was carried out over Ni supported on CeO2 prepared by the co-precipitation method. The influence of metal loadings (2.5, 5 and 10 wt.% Ni) and the reaction conditions such as reaction temperature and feed composition on CO oxidation and oxidation selectivity were evaluated by using dry reformate gas. No other reactions like CO or CO2 methanation, coking, reverse water gas shift (RWGS) reaction is observed in the temperature range of 100-200 A degrees C on these catalysts. Hydrogen oxidation dominates over CO oxidation above the temperature of 200 A degrees C. An increase in oxygen leads to an increase in CO conversion but a simultaneous decrease in the O-2 selectivity. It has been noticed that 5 and 10 % Ni/CeO2 show better catalytic activity towards CO-PROX reaction. These catalysts were characterized by S-BET, XRD, TEM, XPS and H-2-TPR.

Activation of Lattice Oxygen of TiO2 by Pd2+ Ion: Correlation of Low-Temperature CO and Hydrocarbon Oxidation with Structure of Ti1-xPdxO2-x (x=0.01-0.03)

Lattice oxygen of TiO2 is activated by the substitution of Pd ion in its lattice. Ti1-xPdxO2-x (x = 0.01-0.03) have been synthesized by solution combustion method crystallizing in anatase TiO2 structure. Pd is in +2 oxidation state and Ti is in +4 oxidation state in the catalyst. Pd is more ionic in TiO2 lattice compared to Pd in PdO. Oxygen storage capacity defined by ``amount of oxygen that is used reversibly to oxidize CO'' is as high as 5100 mu mol/g of Ti0.97Pd0.03O1.97. Oxygen is extracted by CO to CO2 in absence of feed oxygen even at room temperature which is more than 20 times compared to pure TiO2. Rate of CO oxidation is 2.75 mu mol g(-1) s(-1) at 60 degrees C over Ti0.97Pd0.03O1.97 and C2H2 gets oxidized to CO2 and H2O at room temperature. Catalyst is not poisoned on long time operation of the reactor. Such high catalytic activity is due to activated lattice oxygen created by the substitution of Pd ion as seen from first-principles density functional theory (DFT) calculations with 96 atom supercells of Ti32O64, Ti31Pd1O63, Ti30Pd2O62, and Ti29Pd3O61. The compounds crystallize in anatase TiO2 structure with Pd2+ ion in nearly square planar geometry and TiO6 octahedra are distorted by the creation of weakly bound oxygens. Structural analysis of Ti31Pd1O63 which is close to 3% Pd ion substituted TiO2 shows that oxygens associated with both Ti and Pd ions in the lattice show bond valence sum of 1.87, a low value characteristic of weak oxygen in the lattice compared to oxygens with valence 2 and above in the same lattice. Exact positions of activated oxygens have been identified in the lattice from DFT calculations.

Synthesis and characterization of Fe- and Co-based ferrite nanoparticles and study of the T-1 and T-2 relaxivity of chitosan-coated particles

In pursuit of newer and more effective contrast agents for magnetic resonance imaging, we report in this article the use of biocompatible chitosan-coated ferrite nanoparticles of different kinds with a view to determine their potential applications as the contrast agents in the field of nuclear magnetic resonance. The single-phase ferrite particles were synthesized by chemical co-precipitation (CoFe2O4 and Fe3O4) and by applying ultrasonic vibration (CoFe2O4 and Co0.8Zn0.2Fe2O4). Although magnetic anisotropy of CoFe2O4 nanoparticle leads to finite coercivity even for nanoensembles, it has been reduced significantly to a minimum level by applying ultrasonic vibration. Fe3O4 synthesized by chemical co-precipitation yielded particles which already possess negligible coercivity and remanence. Substitution of Co by Zn in CoFe2O4 increases the magnetization significantly with a small increase in coercivity and remanence. Particles synthesized by the application of ultrasonic vibration leads to the higher values of T-2 relaxivities than by chemical coprecipitation. We report that the T-2 relaxivities of these particles are of two orders of magnitude higher than corresponding T-1 relaxivities. Thus, these particles are evidently suitable as contrast agent for T-2 weighted MR images.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Interdiffusion and the phase boundary compositions in the Co-To system

Diffusion parameters such as the interdiffusion coefficients and the ratio of the tracer diffusion coefficients are calculated in the Co2Ta Laves phase. The activation energy for the interdiffusion coefficients is calculated as 186 +/- 29 kJ/mol. The ratio of tracer diffusion coefficients indicates that Co has higher diffusion rate than that of Ta. This is explained with the help of possible point defects and the crystal structure of the phase: The phase boundary compositions measured in this study is different from the compositions published previously. (C) 2012 Elsevier Ltd. All rights reserved.