Working Methods Paper: Critical considerations with respect to the identification of tin species in the environment

Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation.     

General base catalysis in the decomposition of N-Cl-Valine in aqueous solution

This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10^?4 s^?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc.     

Theory of main chain nematic polymers with spacers of varying degree of flexibility

Main chain liquid crystal polymers are modelled as either worms or jointed rods. In reality they are composed of mesogenic units (rods) linked by spacers with varying degrees of flexibility. We present a molecular model to describe non-homogeneous nematic polymers. The model takes account of molecular parameters, such as the lengths of the mesogenic group and the spacer units, and the interactions between them. The spacers are found to have an order differing from the mesogenic units. If the spacer is not very long and thus in effect is inflexible, one end of the spacer can retain to some extent the orientation of the other end, allowing orientational correlation between spacers mediated by the intermediate mesogenic unit. This is important in giving the chain a global rod-like behaviour as the nematic field becomes strong or the temperature low. The nematic order of the two components (mesogens and spacers), the nematic-isotropic transition as well as the latent entropy are examined. Furthermore, the anisotropic conformations of the polymers are investigated, which show either rod-like or random walk behaviour. Comparison of our results with experiment is found to be satisfactory.     

MgO films grown on yttria-stabilized zirconia by molecular beam epitaxy

MgO films were grown on (0 0 1) yttria-stabilized zirconia (YSZ) substrates by molecular beam epitaxy (MBE). The crystalline structures of these films were investigated using X-ray diffraction and transmission electron microscopy. Growth temperature was varied from 350 to 550 °C, with crystalline quality being improved at higher temperatures. The MgO films had a domain structure: (1 1 1)[1 1 2¯]_MgO(0 0 1)[1 0 0]_YSZ with four twin variants related by a 90° in-plane rotation about the [1 1 1]_MgO axis. The observed epitaxial orientation was compared to previous reports of films grown by pulsed laser deposition and sputtering and explained as resulting in the lowest interface energy.     

Geometric modeling of homoepitaxial CVD diamond growth: I. The {1 0 0}{1 1 1}{1 1 0}{1 1 3} system

Plasma-assisted CVD homoepitaxial diamond growth is a process that must satisfy many stringent requirements to meet industrial applications, particularly in high-power electronics. Purity control and crystalline quality of the obtained samples are of paramount importance and their optimization is a subject of active research. In the process of such studies, we have obtained high purity CVD diamond monocrystals with unusual morphologies, namely with apparent {1 1 3} stable faces. This phenomenon has led us to examine the process of CVD diamond growth and build up a 3D geometrical model, presented here, describing the film growth as a function of time. The model has been able to successfully describe the morphology of our obtained crystals and can be used as a predictive tool to predetermine the shape and size of a diamond crystal grown in a given process configuration. This renders accessible control of desirable properties such as largest usable diamond surface area and/or film thickness, before the cutting and polishing manufacture steps take place. The two latter steps are more sensitive to the geometry of the growth sectors, which will be addressed in a companion paper.Our model, applicable to the growth of any cubic lattice material, establishes a complete mapping of the final morphology state of growing diamond, as a function of the growth rates of the crystalline planes considered, namely {1 0 0}, {1 1 1}, {1 1 0}, and {1 1 3} planes, all of which have been observed experimentally in diamond films. The model makes no claim as to the stability of the obtained faces, such as the occurrence of non-epitaxial crystallites or twinning. It is also possible to deduce transient behavior of the crystal morphology as growth time is increased. The model conclusions are presented in the form of a series of diagrams, which trace the existence (and dominance) boundaries of each face type, in presence of the others, and where each boundary crossing represent a topology change in terms of number of faces, edges and vertices. We validate the model by matching it against crystals published in the literature and illustrate its predictive value by suggesting ways to increase usable surface area of the diamond film.     

Terahertz wave tomographic imaging with a Fresnel lens

We demonstrate three-dimensional tomographic imaging using a Fresnel lens with broadband terahertzpulses.Objects at various locations along the beam propagation path are uniquely imaged on the sameimaging plane using a Fresnel lens with different frequencies of the imaging beam.This procedure allowsthe reconstruction of an object's tomographic contrast image by assembling the frequency-dependentimages.     

Improvement of least-squares finite difference method on simulating slider air bearings in head disk systems

Least-squares finite difference (LSFD) method, one of mesh-free methods, is used to solve slider air bearings problem through discritizing the generalized Reynolds equation into nonlinear systems of algebraic equations. Two approximation schemes for the linearization of these equations are presented and compared. And, some new techniques to search supporting points for the reference node in the mesh-free method were proposed and explored. Therefore, these improvements eliminate some potential limitation of the LSFD method previously published and further facilitate its employment in complex slider models. Advanced step slider as an example of negative pressure sliders is simulated and verified using the improved LSFD mesh-free method in head disk systems.     

Low-energy ion-assisted control of interfacial structures in metallic multilayers

A molecular dynamics method has been used to simulate the argon ion-assisted deposition of Cu/Co/Cu multilayers and to explore ion beam assistance strategies that can be used during or after the growth of each layer to control interfacial structures. A low-argon ion energy of 5–10 eV was found to minimize a combination of interfacial roughness and interlayer mixing (alloying) during the ion-assisted deposition of multilayers. However, complete flattening with simultaneous ion assistance could not be achieved without some mixing between the layers when a constant ion energy approach was used. It was found that multilayers with lower interfacial roughness and intermixing could be grown either by modulating the ion energy during the growth of each metal layer or by utilizing ion assistance only after the completion of each layers deposition. In these latter approaches, relatively high-energy ions could be used since the interface is buried and less susceptible to intermixing. The interlayer mixing dependence upon the thickness of the over layer has been determined as a function of ion energy.     

Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 2006