Preparation and characterization of Cd(0.75)PS(3)A(0.5)(H2O)(y) [A = Na, K and Cs]

Cd(0.75)PS(3)A(0.5)(H2O)(y) [A = Na, K and Cs], synthesized by the ion-exchange intercalation reaction of the insulating layered CdPS3, exhibits interesting electrical properties. The electrical properties are strongly dependent on the extent of hydration of the alkali ion which resides in the interlamellar space. In the potassium and caesium ion-exchanged compounds, y = I, the lattice expansion is similar to 3 Angstrom and the electric response characteristic of a dielectric. In the as prepared A = Na compound, y = 2, the lattice expansion is 5.6 Angstrom, the compound is conducting with a DC conductance of 3 x 10(-5) S cm(-1) at 300 K. Cd0.75PS3Na0.5(H2O)(y), y = 2, on evacuation or on heating looses water, reversibly, to form a y = 1 phase with electrical properties similar to that of the K and Cs ion exchange intercalation compounds.

Barriers to plantation activities in different agro-ecological zones of Southern India

This paper analyses environmental and socio-economic barriers for plantation activities on local and regional level and investigates the potential for carbon finance to stimulate the increased rates of forest plantation on wasteland, i.e., degraded lands, in southern India. Building on multidisciplinary field work and results from the model GCOMAP, the aim is to (1) identify and characterize the barriers to plantation activities in four agro-ecological zones in the state of Karnataka and (2) investigate what would be required to overcome these barriers and enhance the plantation rate and productivity. The results show that a rehabilitation of the wasteland based on plantation activities is not only possible but also anticipated by the local population and would lead to positive environmental and socio-economic effects at a local level. However, in many cases, the establishment of plantation activities is hindered by a lack of financial resources, low land productivity and water scarcity. Based on the model used and the results from the field work, it can be concluded that certified emission reductions such as carbon credits or other compensatory systems may help to overcome the financial barrier; however, the price needs to be significantly increased if these measures are to have any large-scale impact.

A molecular dynamics study and molecular level explanation of pressure dependence of ionic conductivity of potassium chloride in water

Experimental ionic conductivity of different alkali ions in water shows markedly different dependences on pressure. Existing theories such as that of Hubbard-Onsager are unable to explain these dependences on pressure of the ionic conductivity for all ions. We report molecular dynamics investigation of potassium chloride solution at low dilution in water at several pressures between 1 bar and 2 kbar. Two different potential models have been employed. One of the models successfully reproduces the experimentally observed trend in ionic conductivity of K+ ions in water over the 0.001-2 kbar range. We also propose a theoretical explanation, albeit at a qualitative level, to account for the dependence of ionic conductivity on pressure in terms of the previously studied Levitation Effect. It also provides a microscopic picture in terms of the pore network in liquid water.

Synthesis of Co(II), Ni(II) and Cu(II) Complexes from Schiff base Ligand and Reactivity Studies with Thermosetting Epoxy Resin

A hybrid thermosetting maleimido epoxy compound 4-(N-maleimidophenyl) glycidylether (N-MPGE) containing Co(II), Ni(II) and Cu(II) ions was prepared by curing N-MPGE and tetradentate Schiff base Co(II), Ni(II) and Cu(II) complexes. The curing polymerization reaction of N-MPGE with metal complexes as curing agents was studied. The cured samples were studied for thermal stability, chemical (acid/alkali/solvent) and water absorption resistance and homogeneity of the cured systems. The tetradentate Schiff base, 3-(Z)-2-piperazin-1-yl-ethylimino]-1,3-dihydro indol-2-one was synthesized by the condensation of Isatin (Indole-2, 3-dione) with 1-(2-aminoethyl)piperazine (AEP). Its complexes with Co(II), Ni(II) and Cu(II) have been synthesized and characterized by microanalysis, conductivity, Uv-Visible, FT-IR, TGA and magnetic susceptibility measurements. The spectral data revealed that the ligand acts as a neutral tetradentate Schiff base and coordinating through the azomethine nitrogen, two piperazine nitrogen atoms and carbonyl oxygen.

A[Bi3Ti4O13] and A[Bi3PbTi5O16] (A = K, Cs): New n=4 and n=5 members of the layered perovskite series, A[A ' n-1B nO3n+1], and their hydrates

We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi3Ti4O13] and A[Bi3PbTi5O16]for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'n-1BnO3n+1]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Angstrom and loses its doubling [for example, the tetragonal lattice parameters of K[Bi3Ti4O13] and its dihydrate are respectively a = 3900(1)Angstrom c 37.57(2) Angstrom; a 3.885(1) Angstrom, c = 20.82(4) Angstrom]; surprisingly, the cesium analogues do not show a similar change on hydration.

Metal-insulator transition in a degenerate Hubbard model

We have studied the metal-insulator transition at integer fillings in a triply degenerate Hubbard model using the Lanczos method. The critical Coulomb interaction strength U-c, is found to depend strongly on the band filling, with U-c similar to root 3 W (W is the bandwidth) at half filling for this case with threefold degeneracy. We discuss the implications of our results on metal-insulator transitions in strongly correlated systems in general, and on the unusual electronic ground state of the alkali-metal-doped fullerenes, in particular. [S0163-1829(99)11003-8].

Microwave preparation of oxide bronzes

Several vanadium, tungsten, and molybdenum oxide bronzes have been prepared using microwave irradiation. Metal oxides and alkali metal iodides were used as starting materials, Intermittent grinding and inert atmosphere were found to be necessary for the synthesis of most of the bronzes, The reaction temperatures are remarkably lower than those employed for conventional synthetic techniques and the microwave assisted reactions proceed at extremely fast rates. The microwave synthesized bronzes consist of particles having long, rectangular rod-like morphology. (C) 1999 Academic Press.

Synthesis and cation binding properties of new bile acid-based crown ethers

A series of bile acid-based crown ethers (7a-c,12 and 13) were easily constructed from readily available precursors. Measurement of association constants (K-a) with alkali metal picrates in CHCl3 showed that azacrown ethers 7a-c and Chola-Cuowns 12 and 13 show greater binding towards Rb+ and K+. The presence of the aromatic moieties showed subtle changes in the binding properties. Insight II minimized structures show very different conformations of aromatic units in 7a-b and 13.

A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes

Recently, we demonstrated a very general route to monolithic macroporous materials prepared without the use of templates (Rajamathi et al. J. Mater. Chem. 2001, 11, 2489). The route involves finding a precursor containing two metals, A and B, whose oxides are largely immiscible. Firing of the precursor followed by suitable sintering results in a monolith from which one of the oxide phases can be chemically leached out to yield a macroporous mass of the other oxide phase. The metals A and B that we employed in the demonstration were Ni and Zn. From the NiO-ZnO monolith that was obtained by decomposing the precursor, ZnO could be leached out at high pH to yield macroporous NiO. In the present work, we show that combustion-chemical (also called self-propagating) decomposition of a mixture of Ni and Zn nitrates with urea as a fuel yields an intimate mixture of the oxides that can be sintered and leached with alkali to form a macroporous NiO monolith. The new process that we present here thereby avoids the need for a crystalline single-source precursor. A novel and unanticipated aspect of the present work is that the combination of high temperatures and rapid quenching associated with combustion synthesis results in an intimate mixture of wurtzite ZnO and the metastable rock-salt Ni1-xZnxO where x is about 0.3. Leaching this monolith with alkali gives a macroporous mass of rock-salt Ni1-xZnxO, which upon reduction in H-2/Ar forms macroporous Ni and ZnO. There are thus two stages in the process that lead to two modes of pore formation. The first is associated with leaching of ZnO by alkali. The second is associated with the reduction of porous Ni1-xZnxO to give porous Ni and ZnO.

Hydrolytic degradation and diffusion studies on a polyphosphate ester

A polyphosphate ester was synthesized by interfacial polycondensation of bisphenol-A and phenylphosphorodichloridate. Accelerated hydrolytic degradation studies were conducted under alkaline conditions. The effect of concentration of alkali and temperature were monitored. The rate of degradation reached a maximum value at 6 molar sodium hydroxide solution and then reduced. The activation energy for hydrolytic degradation was found to be 45 kcal/mol. Diffusion of alkali into the polymer pellet was studied at various concentrations of alkali and at various temperatures. The rate of diffusion also attained a maximum at 6M NaOH and the activation energy for diffusion process was found to be 12 kcal/mol. (C) 2002 John Wiley Sons, Inc.

Precise measurement of hyperfine intervals using avoided crossing of dressed states

We demonstrate a technique for precisely measuring hyperfine intervals in alkali atoms. The atoms form a three-level system in the presence of a strong control laser and a weak probe laser. The dressed states created by the control laser show significant linewidth reduction. We have developed a technique for Doppler-free spectroscopy that enables the separation between the dressed states to be measured with high accuracy even in room temperature atoms. The states go through an avoided crossing as the detuning of the control laser is changed from positive to negative. By studying the separation as a function of detuning, the center of the level-crossing diagram is determined with high precision, which yields the hyperfine interval. Using room temperature Rb vapor, we obtain a precision of 44 kHz. This is a significant improvement over the current precision of similar to1 MHz.

Nanopatterning on Reconstructed Ceramic Surfaces

The use of reconstructed ceramic surfaces as templates for nanopatterning has been demonstrated recently. This technique differs from the surface decoration by Au on stepped surfaces of alkali halides which has been a topic of intense research in the past. Some of the intriguing aspects related to the physical origin of the phenomena have been considered here. Based on heterogeneous nucleation of Pt vapor on wedged alumina surfaces, it has been shown that the valley sites are the preferred sites for nucleation. However, the hill sites are decorated by the particles in the present study pointing out to a different physical origin for the formation of the nanoparticles. The role of electrostatic energy reduction on the formation of such nanopatterns is discussed.

Properties of concrete containing ultra-fine fly ash

Fly ash and silica fume are two pozzolans that have been widely used for improved concrete strength and durability. Silica fume displays a greater pozzolanic reactivity than fly ash primarily due to its finer particle size. The reactivity of fly ash can be improved by reducing its particle size distribution. This paper discusses the fresh and hardened properties of concrete made with an ultra-fine fly ash (UFFA) produced by air classification. Durability testing for chloride diffusivity, rapid chloride permeability, alkali-silica reaction (ASR), and sulfate attack was also conducted It was found that at a given workability and water content, concrete containing UFFA could be produced with only 50% of the high-range water-reducer dosage required for comparable silica fume concrete. Similar early strengths and durability measures as silica fume concrete were observed when a slightly higher dosage of UFFA was used with a small reduction (10%) in water content.

The effect of host glass on optical absorption and fluorescence of Nd3+ in xNa(2)O-(30-x)K2O-70B(2)O(3) glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Nd3+ has been studied in mixed alkali borate glasses of the type xNa(2)O-(30-x)K2O-69.5B(2)O(3)-0.5Nd(2)O(3) (X = 5,10,15,20 and 25). Various spectroscopic parameters such as Racah (E-1, E-2 and E-3), spin-orbit (xi(4f)) and configuration interaction (alpha, beta) parameters have been calculated. The Judd-Ofelt intensity parameters (Omega(lambda)) have been calculated and the radiative transition probabilities (A(rad)), radiative lifetimes (tau(r)), branching ratios (beta) and integrated absorption cross sections (Sigma) have been obtained for certain excited states of the Nd3+, ion and are discussed with respect to x. From the fluorescence spectra, the effective fluorescence line widths (Deltalambda(eff)) and stimulated emission cross sections (sigma(p)) have been obtained for the three transitions F-4(3/2) --> I-4(9/2), F-4(3/2) --> I-4(11/2) and F-4(3/2) --> I-4(13/2) of Nd3+. The stimulated emission cross section (sigma(p)) values are found to be in the range (2.0-4.8) x 10(-2)0 cm(2) and they are large enough to indicate that the mixed alkali borate glasses could be potential laser host materials.