Studies of cyclic and linear poly(dimethyl siloxanes): 5. Diffusion behaviour in dilute solution

The diffusion coefficients of cyclic and linear oligomeric and polymeric dimethyl siloxanes, containing number-average numbers of skeletal bonds in the range $\text{6 <}\text{n}\text{?}{}_{\mathrm{n}}\text{< 650}$, have been measured in toluene solution at 298K. Impermeable diffusion behaviour was observed for all the siloxanes studied, in agreement with previous findings for ethylene oxide and hexamethylene oxide oligomers and polymers. The ratio of the friction coefficients $\text{f}{}_{\mathrm{r}}\text{f}{}_{\mathrm{l}}$ for the ring (r) and linear (l) dimethyl siloxanes was found to be $\text{8}\text{3κ}$ (within the limits of experimental error) over the whole range of molecular weights studied. Values of the expansion factor α_f for the linear poly(dimethyl siloxanes) (obtained from the diffusion measurements) were found to be approximately equal to the corresponding values for α_η (found previously by viscometric studies) for small values of the excluded volume parameter z; and α_f was larger than α_η for large z, as predicted by first-order perturbation theory. Mean-square radii of gyration 〈s²_G〉 were calculated from the diffusion data for both cyclic and linear poly(dimethyl siloxanes) assuming Gaussian statistics, and found to be in good agreement with the corresponding values obtained by neutron scattering. However, the values of 〈s²_G,l〉 for the short chain poly(dimethyl siloxanes) did not agree with the corresponding values of 〈s²_O,l〉, calculated using the rotational isomeric state model of Flory, Crescenzi and Mark. This discrepancy is thought to arise from deviations from Gaussian behaviour, and considerably better agreement between experiment and theory was achieved by using appropriate values of a function ψ_l(x), which relates radii of gyration and impermeable hydrodynamic diffusion radii.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

Using multiple‐mode models for fitting and predicting the rheological properties of polymeric melts. II. Single and double step‐strain flows

Several classes of multiple‐mode rheological constitutive equations are examined for predicting the viscoelastic flow properties of a typical polymer melt in single and double step‐strain flows. The phenomenological parameters appearing in these models have been obtained by the fitting of experimental data taken in small‐amplitude oscillatory shear and steady shear flows. The performance of the models for predicting the experimental data in the step‐strain experiments is examined in detail. Specifically, we examine whether or not mode coupling is necessary to describe the experimental behavior under step‐strain flows. Furthermore, it is demonstrated that the reversing double step‐strain experiment is a very powerful tool for testing viscoelastic constitutive equations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Aerodynamics and aerosol particle deaggregation phenomena in model oral-pharyngeal cavities

The results of numerical simulations of the aerodynamics and of solid aerosol deaggregation phenomena arising in the process of airflow through various model human oropharyngeal cavities are reported. Special attention is given to the relevance of these simulations to the inhalation of dry-powder therapeutic aerosols. Several two- and three-dimensional mouth and throat geometries (terminating just beyond the larynx) are considered. Cross-sectional area-averaged viscous stress values are numerically determined as a function of distance from the mouth opening. These values, ranging from approximately 10 to 500 dyn cm⁻², are compared with estimates of Van der Waals attractive forces per unit area of particle-particle contact so as to evaluate the ability of the flowing airstream to deaggregate aerosol particles that enter the mouth in an aggregated state (held together principally by Van der Waals attractive forces). Estimates of airstream viscous stress differ markedly depending on whether the geometry is two- or three-dimensional. Quantitative differences between flow in a 90°-bend model and an oropharyngeal geometry numerically reconstructed from a cast of a human mouth and throat are especially significant in regards to the ability of the airstream to break apart particle agglomerates. For all geometries it is observed that increasingly smaller particle agglomerates may potentially be separated as the airflow rate increases from 30 to 2001 min⁻¹. At the highest airflows, aggregated particles of diameter near to or even below 1 μm may potentially be separated by the airflow. If separation of particle agglomerates is to occur, it appears far more likely to take place in the throat than in the mouth. This is especially apparent for the more physiologically faithful oropharyngeal geometries considered.     

Direct synthesis of hydrogen peroxide from H2 and O2 using zeolite-supported Au catalysts

The direct synthesis of hydrogen peroxide from H₂ and O₂ using zeolite-supported Au catalysts is described and their activity is contrasted with silica- and alumina-supported Au catalysts. Two zeolites were investigated, ZSM-5 and zeolite Y. The effect of calcination of these catalysts is studied and it is found that for uncalcined catalysts high rates of hydrogen peroxide formation are observed, but these catalysts are unstable and lose Au during use. Consequently, reuse of these catalysts leads to lower rates of hydrogen peroxide formation. However, catalysts calcined at 400 °C are more stable and can be reused without loss of gold. The use of zeolites as a support for Au gives comparable rates of hydrogen peroxide formation to alumina-supported Au catalysts and higher rates when compared with silica-supported catalysts. prepared using a similar method. Zeolite Y-supported catalysts are more active than ZSM-5-supported catalysts for the stable calcined materials. It is considered that the overall activity of these supported catalysts may be related to the aluminium content as the activity increases with increasing aluminium content.     

脉冲涡流和电磁声换能器双探头无损检测

在许多情况下，只应用一种NDT技术存在不足，这就迫使NDT操作人员使用一种以上的技术以保证检测出危害被检物使用寿命或功能的缺陷。但分别实施多种技术的检测，就会延长检验时间。介绍了一种新的NDT设施，采用两种不同的非接触无损检测技术进行互补，即电磁声换能器（EMAT）和脉冲涡流（PEC）探头。检测结果表明，脉冲涡流和电磁声换能器因是非接触，所以可应用于材料生产过程中的自动在线检验，也可用于在役检验。     

Dual Verbal Elicitation: The Complementary Use of Concurrent and Retrospective Reporting Within a Usability Test

Verbal protocols are the primary tool for understanding users' task-solving behaviors during usability testing. A qualitative study that examined the utility of combining a concurrent and retrospective think-aloud within the same usability test is described. The results indicate that although there was significant overlap between the types of utterances produced during each think-aloud, the retrospective phase produced more verbalizations that were relevant to usability analysis, for example, helpful self-assessments of performance, yielding insights into the impact of encountered difficulties. However, a small number of less desirable utterance types emerged: hypothesising, rationalizing, and forgetting. When used together, both methods contributed to an understanding of usability issues; the concurrent phase yielded more usability issues overall, and the retrospective data improved the understanding of these by (a) reinforcement: users highlighted the impact of an issue on their experience, (b) elaboration: users would provide causal explanations of encountered difficulties, and (c) context: users provided information about the product's context of use.     

An EM approach to mineral analysis using natural gamma rays

We describe here a method for the analysis of materials on a conveyor belt using the natural gamma spectra collected with a BGO (Bismuth Germanate) gamma ray detector. This detector collects gamma ray emissions from the Potassium (K), Uranium (U), and Thorium (Th) atoms in the materials. Based on these data, and using a Poisson model for the data generation, a statistical model is proposed and an approximate maximum likelihood (ML) technique based on the expectation-maximization (EM) algorithm is then used to estimate the amount of each of the three elements in the material. The statistical model is further refined to incorporate parameters of drift in the detector and an estimation technique for this is developed and tested against real data. The Cramér–Rao lower bounds for the estimators are calculated.     

A Managed IPv6 Transitioning Architecture for Large Network Deployments

With IPv6 transitioning still in a relative state of flux, the need has emerged for methods to control this crucial aspect of IPv6 deployments. This article makes the case for transitioning architectures as a realistic solution to this issue, specifically within large-scale networks. The Site Transitioning Architecture (STA) supports the deployment, operation, and management of IPv6 transitioning mechanisms. The authors provide an overview of the STA's design and operation, noting that its flexible, simple, and secure architecture is suitable for the duration of the IPv6 deployment process, regardless of the underlying network environment.