Glass transitions in hydrogen-bonded polymer complexes

Mutual precipitates of poly (N, N-dimethyl acrylamide) and poly (4-hydroxystyrene) were collected from dioxane, methanol, or acetone. The glass transition (T_g) temperatures of the precipitates are higher than the weight-average values. Clear films cast from dimethylformamide solutions have lower T_g values. Complexation also occurred between poly (ethyl oxazoline) and poly (4-hydroxystyrene) in dioxane and between poly (vinyl pyrrolidone) and poly (4-hydroxystyrene) in methanol. Again, the glass transition temperatures of the precipitates are higher than the values for the blend films. The ΔC_p values associated with the glass transitions of the complexes are smaller than those of the blends having the same compositions. Negative excess heat capacities of mixing have been observed for several precipitates.     

An experiment with arithmetic precision in linear algebra computations

Several techniques for experimental determination of floating point precision in practical computations are examined, and applied to linear algebra algorithms. These techniques are simple enough to be directly applicable to existing production codes, requiring a very limited amount of software on many machines, and yet they yield interesting information on the numerical precision of a computation. Our choice of linear algebra algorithms includes a direct solver (namely the MA32 program from the Harwell Library) and several variants of preconditioned conjugate gradients (the methods DIAG, INV, MINV and POL of Reference 1). The results may be of interest as method selection criteria, and thus complement Mflop performance data available from several sources.     

Comparison of four quantification methods for the determination of PCB in transformer oils

The analysis of PCB in transformer oils has been achieved with three HRGC/ECD based methods, proposed by the International Electrotechnical Commission (IEC/TC 10), by the Comité Européen de Normalisation (CEN/TC 19/WG 22) and by the Deutsches Institut für Normung (DIN 51 527). The same clean-up, described in the CEN/TC 19/WG 22, has been used for all the samples, allowing a comparison of the quantification procedure only. The total chlorine content has also been determined with X-ray fluorescence. These different methods of quantification are compared and their application for legislative purposes is discussed.Dedicated to Professor Dr Dieter Klockow on the occasion of his 60th birthday     

Organometallic complexes with biological molecues,part 3. in vivo cytotoxicity of diorganotin (IV) chloro and triorganotin (IV) chloro derivatives of penicillin g on chromosomes of aphanius fasciatus (pisces,cyprinodontiformes)

In order to obtain a continuous source of mitotic metaphases, gill tissue of Aphaius fasciatus (Pisces, Cyprinodontiformes) has been successfully employed. Results gathered after exposure of fish to R₂SnClpenG, R₃SnClpenGNa, to the parents R₂SnCl₂, R₃SnCl and to penGNa (penGNa = penicillinGNa; R = methyl, butyl and phenyl) suggest that both the parent organotin (IV) chloride and organotin (IV) chloropenG derivatives are toxic while penGNa exerts no significant toxic activity. Essentially, all of the chromosome abnormalities are classifiable as irregularly staining of chromosomes, breakages, side-arm bridges or pseudochiasmata.     

Photoinduced electron transfer variables: rigidity or orientation?

The relatives photoreactives of bridged-ring systems 1, 3, 5-X and 6-X (X ≡ Cl or Br) have been studied at 254 nm in acetic acid. The formation of photosolvolysis product was rationalized in terms of photoinduced intramolecular electron transfer (ET) processes. The relative ease of ET in these donor—bridge—acceptor model system was analyzed in terms of known ET variables including free-energy changes, orientation effects and ridigity effects. The observed relative photoreactivities agreed better with the calculated free-energy changes when relative rigidities of the electron acceptor termini were evaluated. In general, the more rigid system were more photoreactive.     

Manifestation of biquadratic coupling in the smectic C* phase soft mode dielectric response

The soft mode dielectric response of three ferroelectric chiral smectic C* substances is studied in the vicinity of the smectic C*-smectic A* phase transition. For some substances the soft mode dielectric strength exhibits a pronounced anomaly in the C* phase just below the phase transition. We show how this anomaly can be systematically correlated with a corresponding anomaly in the experimentally determined ratio of spontaneous polarization over tilt. By comparing the experimental results with the theoretical predictions of an extended Landau model, we demonstrate how the crossover behaviour of the system can be interpreted as being the consequence of the presence of a biquadratic coupling between tilt and polarization in the Landau free-energy of the system.     

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.     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.