An aqueous-solution based low-temperature pathway to synthesize giant dielectric CaCu3Ti4O12-Highly porous ceramic matrix and submicron sized powder

A simple, cost-effective and environment-friendly pathway for preparing highly porous matrix of giant dielectric material CaCu3Ti4O12 (CCTO) through combustion of a completely aqueous precursor solution is presented. The pathway yields phase-pure and impurity-less CCTO ceramic at an ultra-low temperature (700 degrees C) and is better than traditional solid-state reaction schemes which fail to produce pure phase at as high temperature as 1000 degrees C (Li, Schwartz, Phys. Rev. B 75, 012104). The porous ceramic matrix on grinding produced CCTO powder having particle size in submicron order with an average size 300 nm. On sintering at 1050 degrees C for 5 h the powder shows high dielectric constants (>10(4) at all frequencies from 100 Hz to 100 kHz) and low loss (with 0.05 as the lowest value) which is suitable for device applications. The reaction pathway is expected to be extended to prepare other multifunctional complex perovskite materials. (C) 2010 Elsevier B.V. All rights reserved.

Dissolution properties of BaTiO3 nanoparticles in aqueous suspensions

Dissolution of barium ion from aqueous suspensions of commercial nano-sized barium titanate powders (BaTiO3) has been studied at various pH values, solids loading, different time intervals and different electrolyte concentrations. Zeta potential measurements at various pH values and Fourier transform infrared spectroscopy study were also carried out to know the surface behaviour. Dissolution of Ba2+ depends on the suspension pH and stirring time period. The iso-electric points were found at 3.4 and 12.2 for as-received BaTiO3 powder and 2.3 for the leached BaTiO3. The Ba2+-leached BaTiO3 suspension retards further leaching of Ba2+ ions at different pH values, which favours the achievement of stable suspension.

A novel (main chain) (side chain) polymeric peroxide: Synthesis and initiating characteristics of poly(alpha-(tert-butylperoxymethyl)styrene peroxide)

A novel (main chain)-(side chain) vinyl polyperoxide, poly(alpha-(tert-butylperoxymethyl)styrene peroxide) (MCSCPP), an alternating copolymer of alpha-(tert-butylperoxymethyl)styrene (TPMS) and oxygen, has been synthesized by the oxidative polymerization of TPMS. The MCSCPP was characterized by H-1 NMR, C-13 NMR, IR, DSC, EI-MS, and GC-MS studies. The overall activation energy (E(a)) for the degradation of MCSCPP was found to be 27 kcal/mol. Formaldehyde and alpha-(tert-butylperoxy)acetophenone (TPAP) were identified as the primary degradation products of MCSCPP; TPAP was found to undergo further degradation. The side chain peroxy groups were found to be thermally more stable than those in the main chain. Polymerization of styrene in the presence of MCSCPP as initiator, at 80 degrees C, follows classical kinetics. The presence of peroxy segments in the polystyrene chain was confirmed by both H-1 NMR and thermal decomposition studies. Interestingly, unlike other vinyl polyperoxides, the MCSCPP initiator shows an increase in molecular weight with conversion.

Metal-Free Deprotection of Terminal Acetonides by Using tert-Butyl Hydroperoxide in Aqueous Medium

Employing aqueous tert-butyl hydroperoxide (70%) as an inexpensive reagent a useful methodology for the regioselective and chemoselective deprotection of terminal acetonide groups in aqueous medium is developed. A variety of acetonide derivatives on reaction with aqueous tert-butyl hydroperoxide in water:tert-butanol (1:1) furnish the corresponding acetonide deprotected diols in good yields. A large number of acid labile protecting functional groups and other functional moieties were found to be unaffected under the conditions employed for the present deprotection. This method has been successfully applied to sugar derivatives.

Reactivities of aluminium and aluminium-magnesium alloy powders in polymeric composites

Polymeric compositions containing Al-Mg alloys show higher reactivities, in comparison with similar compositions containing aluminium. This is observed irrespective of the amount of oxidizer, type of oxidizer used, type of polymeric binder, and over a range of the particle sizes of the metal additive. This is evident from the higher calorimetric values obtained for compositions containing the alloy, in comparison to samples containing aluminium. Analysis of the combustion residue shows the increase in calorimetric value to be due to the greater extent of oxidation of the alloy. The interaction between the polymeric binder and the alloy was studied by coating the metal particles with the polymer by a coacervation technique. On ageing in the presence of ammonium perchlorate, cracking of the polymer coating on the alloy was noticed. This was deduced from differential thermal analysis experiments, and confirmed by scanning electron microscopic observations. The increase in stiffness of the coating, leading to cracking, has been traced to the cross-linking of the polymer by magnesium.

Oxidation of Sulfur Dioxide in Aqueous Suspensions of Activated Carbon

Sulfur dioxide in aqueous solutions at low pH levels exists both in molecular SO2(aq) and in hydrolyzed ionic form HSO3-. Experiments indicate that only HSO3- is the reacting species in the oxidation catalyzed by activated carbon, while SO2(aq) deactivates by competing with HSO3 for the active sites of the catalyst particles. A mechanism is proposed and a rate model is developed that also accounts for the effect of sulfuric acid (product of the oxidation) on the solubility of sulfur dioxide. It predicts first order in HSO3-, half order in dissolved oxygen, and a linear deactivation effect of SO2(aq), which are confirmed by experimental data. The deactivation reaches a constant level corresponding to saturation of the active sites by SO2(aq). Activation energy for the oxidation is 93.55 kJ mol(-1) and for deactivation is 21.4 kJ mol(-1).

(PEG)(x)NH4ClO4: A new polymeric fast proton conductor

A new polymer electrolyte (PEG)(x) NH4ClO4(x = 5, 10, 15, 20) has been prepared that shows protonic conduction. The room temperature conductivities are of the order of 10(-7) S/cm, and increase with decrease in salt concentration. NMR line width studies indicate fairly low glass transition temperatures of the polymer salt complexes.

Role of Li+ ions in corrosion behaviour of 8090 Al-Li alloy and aluminium in pH 12 aqueous solutions

The influence of Li+ ions on the corrosion behaviour of the Al-Li alloy 8090-T851 and of commercially pure aluminium in aqueous solutions at pH 12 was studied by weight loss and electrochemical polarisation methods. The inhibiting role of Li+ was concentration dependent, corrosion rate decreasing lineally with log[Li+] in the concentration range 10(-4)-10(-1) mol L(-1). A change from general to pitting corrosion was evident from scanning election microscopy studies. Polarisation studies revealed that Li+ primarily acts as an anodic inhibitor (passivator). Passive film formation and stability also become more feasible with increasing Li+ concentration. Fitting potential was dependent on the Cl- ion concentration in the solution. Both materials were affected similarly by the presence of Li+ ions, the corrosion rate of the alloy being slightly lower. This is attributed to the lithium in the alloy acting as a source of lithium for passive film formation. (C) 1995 The Institute of Materials.

Al2O3---ZrO2 composite coatings for thermal-barrier applications

Graded alternate layers of Al2O3 and 8% Y2O3-ZrO2 and their admixtures were plasma sprayed onto bond-coated mild steel. They were evaluated for thermal-shock resistance, thermal-barrier characteristics, hot corrosion resistance (molten NaCl corrodant) and depth of attack, adhesion strength and the presence of phases. Although front-back temperature drops of 423-623 K were observed, some of the coatings showed good adherence even after 100 thermal shack cycles. In the sequence of the graded layers, the oxide which is directly in contact with the bond coat appears to influence the properties especially in coatings of 150 and 300 mu m thickness. Molten NaCl readily attacks the films at high hot-face temperatures (1273 K for 1 h) and the adhesive strength falls significantly by 50-60%. Diffusion of alkaline elements is also found to depend on the chemical composition of the outer coating directly facing the molten corrodant. (C) 1997 Elsevier Science Limited.

Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects

Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.

Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD

Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams'' have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1: 3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for low-pressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis ( and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.

Synthesis, crystal structure and magnetic properties of a polymeric copper(II) Schiff-base complex having binuclear units covalently linked by isonicotinate ligands

The polynuclear copper(II) complex [{Cu2L(O2CC5H4N)}. C2H5OH](x) (1), where H3L is a 1∶2 Schiff base derived from 1,3-diaminopropan-2-ol and salicylaldehyde, has been prepared and structurally characterized. The structure consists of a one-dimensional zigzag chain in which the binuclear [Cu2L](+) units are covalently linked by isonicotinate ligands to give a syndiotactic arrangement of the copper ions protruding outside the chain. In the basic unit, the copper(II) centres are bridged by an alkoxo and a carboxylato ligand, giving a Cu ... Cu distance of 3.492(3) Angstrom and a Cu-O-Cu angle of 130.9(2)degrees. While one copper centre has a square-planar geometry, the other copper is square-pyramidal with the pyridine nitrogen being the axial ligand. The visible electronic spectrum of 1 shows a broad d-d band at 615 nm. The complex shows a rhombic X-band EPR spectral pattern in the polycrystalline phase at 77 K. Magnetic susceptibility measurements in the temperature range 22 to 295 K demonstrate the antiferromagnetic behaviour of 1. A theoretical fit to the magnetic data is based on a model assuming 1 as an equimolar mixture of copper atoms belonging to an antiferromagnetically coupled one-dimensional Heisenberg chain with the other copper atoms outside the chain behaving like paramagnetic centres.

Characterization of electrochemically deposited Cu-Ni black coatings

Electrochemically deposited Cu-Ni black coatings on molybdenum substrate from ethylenediaminetetraacetic acid (EDTA) bath solution are shown to exhibit good optical properties (alpha = 0.94, epsilon = 0.09). The deposit is characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Cu is present in metallic and +2 oxidation states in the as-prepared Cu-Ni black coating, whereas Ni2+ as well as Ni3+ species are observed in the same coating. Cu and Ni are observed in their metallic state after 10 and 20 min sputtering. X-ray initiated Auger electron spectroscopy (XAES) of Cu and Ni also agrees well with XPS investigations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Accelerated weathering of distribution class polymeric insulators

This paper deals with the long-term accelerated weathering of 11 kV polymeric insulators for 25000 h. Polymeric insulators were continuously subjected to accelerated weathering in a specially designed multistress-aging chamber under UV radiation, temperature and electric stress. Chemical, physical and electrical changes due to degradation have been assessed using various techniques. Some of the interesting results observed indicate that there is a significant reduction in the content of low molecular weight molecules, hydrophobicity was dynamic in nature and there is a significant increase in the surface roughness and oxidation levels with respect to the duration of the weathering.