Time-dependent X-ray absorption spectroscopic (XAS) study on the transformation of zinc basic salt into bis(N-oxopyridine-2-thionato) zinc (II)

Solid transchelation reaction was established for the synthesis of bis(N-oxopyridine-2-thionato) zinc (II), commonly known as zinc pyrithione (ZPT), to control particle size using zinc basic salt (ZBS) and aqueous sodium pyrithione solution. Distinguished from ZPT particles prepared by usual precipitation reaction, the obtained ZPT nanoparticles exhibited very narrow size distribution. X-ray absorption spectroscopy (XAS) at Zn K-edge was systematically examined to elucidate time-dependent local structural evolution during solid transchelation reaction. X-ray absorption near edge structure (XANES) analysis clearly revealed that local environment around zinc atoms transformed into pentahedron as reaction proceeded. Based on quantitative X-ray diffraction and XANES analysis, we made structural models. Theoretical XAS spectrum calculated with FEFF code could reproduce experimental one, suggesting that XAS analysis could be very powerful tool to probe phase transformation. Furthermore, according to extended X-ray absorption fine structure (EXAFS) fitting results, Zn-O distance in reaction products gradually increased from 1.96 to 2.07 angstroms, suggesting that zinc atoms bounded with oxygen ones in ZBS were transchelated with pyrithione ligands. This study could be a strong evidence for the usefulness of XAS to study time-dependent structural transformation of nanocrystalline materials.     

Ferromagnetic signal in nanosized Ag particles

A new technique using an inductively coupled plasma reactor equipped with a liquid-nitrogen cooling system was developed to prepare Ag nanoparticles. The magnetic signal from these Ag particles with diameters of 4 nm showed, surprisingly, a signal with combined ferromagnetic and diamagnetic components, in contrast to the signal with only one diamagnetic component from bulk Ag. The same technique was used to prepare the Ag/Cu nanoparticles, which are Ag nanoparticles coated with a Cu layer. Compared to the Ag nanoparticles, these showed a greatly enhanced superparamagnetic signal in addition to the same value of the ferromagnetism. The comparison between the Ag and the Ag/Cu nanoparticles indicated that the ferromagnetic components are a common feature of Ag nanoparticles while the greatly enhanced paramagnetic component of Ag/Cu, which dominates over the background diamagnetic component from the Ag core, is from the outer Cu shell.     

Purity evaluation of carbon nanotube materials by thermogravimetric, TEM, and SEM methods

Raw and purified samples of carbon nanotubes are considered as multicomponent systems with a distribution of carbonaceous, amorphous, multishell graphitic particles and nanotubes, together with the particles of metal compounds from the catalyst. With respect to the carbon nanotube fractions, a distribution of size, defect concentrations, and functionalities needs to be taken into account. In order to address the problem of quantitative evaluation of purity it is necessary to measure the quality and distribution of the carbon nanotubes. In this research conventional and high resolution thermogravimetry are applied to quantify different fractions of carbonaceous and metallic materials in raw and moderately purified single walled and multiwalled carbon nanotubes. For each oxidized fraction, defined by careful line shape analysis of the derivative thermogravimetric curves (DTG), the temperature of maximum rate of oxidation, the temperature range for this oxidation, related to the degree of homogeneity, and the amount of associated material is specified. The attribution of carbonaceous materials to each fraction in the distribution was based on SEM and TEM measurements and the literature. The MWNT purified sample with 1.6 wt% metal oxide was investigated by high resolution thermogravimetry (HRTG). The quantitative assessment for the carbonaceous fractions was 25 wt% of amorphous and high defect carbonaceous materials including nanotubes, 54 wt% MWNT and 20 wt% multishell graphitic particles. A qualitative evaluation of these fractions was obtained from the SEM and TEM images and supports these results. The accuracy of the values, taking into account other measurements performed on the same batch of material, should be more sensible than +/-4 wt%.     

EFFECT OF CARBON AND BORON ON MICROSTRUCTURE AND MECHANICAL PROPERTIES OF A SINGLE CRYSTAL SUPERALLOY RR 2072

Carbon and boron have been considered to strengthen grain boundaries that might form during single crystal casting. In this study the effect of boron on solidification behavior and creep properties of the carbon doped single crystal RR 2072 has been investigated. In order to understand solidification behavior with boron addition, the solid/liquid interface morphology and solidification microstructare were examined with solidification rate. The relationship between microstructaral evolution and creep properties of the carbon and boron modified single crystal has been also investigated.     

Adhesion of edible oils to food contact surfaces

Adhesion of oils and fatty food products to packages is an important storage problem, because it increases product-package interactions that alter quality. Reducing such adhesion would also allow savings in recycling and cleaning processes. The aim of our work was to test if some thermodynamical adhesion models were correlated to edible oils’ bulk adhesion as measured experimentally. Food-contact surfaces were low-density polyethylene, polyethylene teraphthalate, stainless steel, and glass. The Young-Dupré equation and five models of adhesion from the literature were used to calculate solids’ surface tension and the thermodynamical work of adhesion (Wa). The dispersive, polar, acid-base, and hydrogen surface tension components of oils and solids were calculated. The experimental adhesion, or amount of edible oils remaining on solid surfaces after contact, was found to be correlated to Young-Dupré Wa, involving contact angle measured by specially designed image analysis technique. Two models, involving, respectively, surface tension’s hydrogen component and a linear dependence of Wa^p on the liquid polar surface tension component, fitted best with oil bulk adhesion as measured experimentally. Our theoretical approach to fatty food material adhesion seems, so far, consistent to predict global residues of edible oils on solid surfaces.     

Synthesis and characterization of polyimides from 1,4-bis[4-(n-alkyloxy)phenyloxy]pyromellitic dianhydrides and 4,4'-oxydianiline

Summary New pyromellitic dianhydrides having (n-alkyloxy)phenyloxy (-O-Ph-O-n-C_mH_2m+1, m=1,4,8,12) side chains were synthesized and polymerized with 4,4'-oxydianiline (ODA) in NMP at room temperature. Imidization was carried out using triethylamine and acetic anhydride. The synthesized polyimides (C_m-OPIs) were characterized and their properties were measured and discussed in respect to the effects of side chains. Inherent viscosities of the polymers were in the 0.46 – 0.68 dL/g range. All the polymers were highly soluble in N-methylpyrrolidinone (NMP) and slightly soluble in DMSO, m-cresol, DMF and concentrated H₂SO₄ at room temperature. TGA pyrograms showed two-step degradation. In DSC thermograms the polymers exhibited T_g's between 219°C and 305°C and melting points near 350°C were observed in C₈- and C₁₂-OPIs. Wide-angle X-ray diffractometry for as-polymerized samples revealed very low crystallinities and layered structures which were better developed in the polymers with longer side chains. Received: 11 November 1997/Revised version: 4 December 1997/Accepted: 9 December 1997     

Adsorption equilibria of chloropentafluoroethane on activated carbon powder

An equilibrium study was conducted on the adsorption of chloropentafluoroethane (CFC-115, CF₃CF₂Cl) on activated carbon powder between 298.15 K and 373.15 K. Experimental data were fitted with several isotherm equations. Among the twoparameter equations, the BET equation showed the best results over the entire relative pressure range studied. When the pressure range was divided into two regions, a better result was obtained by applying the Langmuir equation in the lower pressure range and the BET equation in the higher relative pressure region. Among the threeparameter equations, the Langmuir-Freundlich equation gave better results than the RedrichPeterson equation. The isosteric heat of adsorption of CFC-115 on the activated carbon powder was estimated. It was found to have the same order of magnitude with the heat of condensation, which indicates that the adsorption was primarily due to physical forces.     

Molecular catalysis in liquid multiphase systems

The possibilities of using liquid-liquid biphase or multiphase reaction systems for organometallic catalysis are discussed. An overview of important industrial two-phase processes, including – among others – the Shell α-olefin process and the Ruhrchemie/Rhône Poulenc process for propene-1 hydroformylation, is given. The special effects of the aqueous environment are discussed through the examples of the catalytic isomerization of allylbenzene and the hydrogenation of unsaturated aldehydes (pH-effects), the catalyzed deuteriation of itaconic acid from D₂O as the deuterium source (micellar effects), the reduction of carbon dioxide to formic acid and the spontaneous formation of phosphonium salts (stabilizing effects of hydration and protonation).     

High temperature mechanical properities and creep crack initiation of DS CM186LC for nozzle guide vane

The second generation DS alloy, CM186LC is used in the as-cast and double aged condition which has creep-rupture properities equivalent to the first generation single crystal alloys CMSX-2 and CMSX-3. In production, cast vane components have to be subjected to a brazing treatment for joining into pairs. The effect of the brazing treatment and modified brazing treatment (heat treatment) on mechanical properities at high temperature was studied in accordance with microstructure. Brazing treatments gave no effect on tensile properities and creep failure mode of DS CM186LC, although a small decrease in stress-rupture life was observed. Creep failure was related to the solidified microstructure. Creep cracks began at the grain boundary normal to the applied stress, especially at the γ/γ’ eutectic phase on grain boundaries. Most of γ/γ’ eutectics which had solidified at the last stage of casting, had microporosity which became a crack initiation site during creep. MC carbide reaction with the matrix γ was observed in the creep failed specimens.     

Autonomous cutting parameter regulation using adaptive modeling and genetic algorithms

In this research, a turning process is modeled adaptively by a backpropagation, multilayered neural network with an iterative learning method, and cutting parameters of the process model are optimized through genetic algorithms (GAs). Some constraints were given on the input conditions and the process outputs to provide for the desired surface integrity and to protect the machine tool. Introducing penalty values, which are included in the fitness evaluation of the GAs, we can solve such a constrained problem. Experimental results show that the neural network has the ability to model the turning process on-line, and such cutting conditions as spindle speed and feed rate can be adaptively regulated for maximizing the material removal rate using the GAs.