Kinetics of two-step anionic polymerization

This article deals with the kinetics of two-step anionic polymerization by way of a non-steady state method. Several molecular parameters can be evaluated using the formulae developed. A bimodal molecular weight distribution function for the resulting polymer is derived from the set of kinetic differential equations, which is in agreement with the experimental data reported.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Extrapolation of fuzzy values from incomplete data bases

This paper presents different approaches which enable a data base management system to obtain a plausible fuzzy estimate for an attribute value of an item for which the information is not explicitly stored in the data base. This can be made either by a kind of analogical reasoning from information about particular items or by means of expert rules which specify the (fuzzy) sets of possible values of the attribute under consideration, for various classes of items. Another kind of expert rules enables the system to compute an estimate from the attribute value of another item provided that, in other respects, this latter item sufficiently resembles the item, the value of which we are interested in; then these expert rules are used either for controlling the analogical reasoning process or for enlarging the scope of application of the first kind of expert rules. The different approaches are discussed in the framework of possibility theory.     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Uncertainty,belief, and probability1

We introduce a new probabilistic approach to dealing with uncertainty, based on the observation that probability theory does not require that every event be assigned a probability. For a nonmeasurable event (one to which we do not assign a probability), we can talk about only the inner measure and outer measure of the event. In addition to removing the requirement that every event be assigned a probability, our approach circumvents other criticisms of probability-based approaches to uncertainty. For example, the measure of belief in an event turns out to be represented by an interval (defined by the inner and outer measures), rather than by a single number. Further, this approach allows us to assign a belief (inner measure) to an event E without committing to a belief about its negation -E (since the inner measure of an event plus the inner measure of its negation is not necessarily one). Interestingly enough, inner measures induced by probability measures turn out to correspond in a precise sense to Dempster-Shafer belief functions. Hence, in addition to providing promising new conceptual tools for dealing with uncertainty, our approach shows that a key part of the important Dempster-Shafer theory of evidence is firmly rooted in classical probability theory. Cet article présente une nouvelle approche probabiliste en ce qui concerne le traitement de l'incertitude; celle-ci est basée sur l'observation que la théorie des probabilityés n'exige pas qu'une probabilityé soit assignée à chaque événement. Dans le cas d'un événement non mesurable (un événement pour lequel on n'assigne aucune probabilityé), nous ne pouvons discuter que de la mesure intérieure et de la mesure extérieure de l'évenément. En plus d'éliminer la nécessité d'assigner une probabilityéà l'événement, cette nouvelle approche apporte une réponse aux autres critiques des approches à l'incertitude basées sur des probabilityés. Par exemple, la mesure de croyance dans un événement est représentée par un intervalle (défini par la mesure intérieure et extérieure) plutǒt que par un nombre unique. De plus, cette approche nous permet d'assigner une croyance (mesure intérieure) à un événement E sans se compromettre vers une croyance à propos de sa négation -E (puisque la mesure intérieure d'un événement et la mesure intérieure de sa négation ne sont pas nécessairement une seule et unique mesure). II est intéressant de noter que les mesures intérieures qui résultent des mesures de probabilityé correspondent d'une manière précise aux fonctions de croyance de Dempster-Shafer. En plus de constituer un nouvel outil conceptuel prometteur dans le traitement de l'incertitude, cette approche démontre qu'une partie importante de la théorie de l'évidence de Dempster-Shafer est fermement ancrée dans la theorie classique des probabilityés.     

Reaction steady states and stationary states in modelling semi-batch enzyme hydrolysis

Dimensionless material balance equations describing an uninhibited enzyme hydrolysis process in a semi-batch reactor (i.e. fed-batch reactor) are formulated; numerical solution of these equations provided concentration profiles of the enzyme-substrate complex by using published kinetic parameters. The unrestricted values obtained are compared with estimates based separately on the reaction steady state and stationary state assumptions. Results are discussed in terms of the enzyme/substrate inventory used and it is found that the reaction steady state is a satisfactory approximation only when this ratio is sufficiently small. The stationary state may be a better approximation at other values, particularly when enzyme is added to substrate or when an empty tank is being filled. Reaction yields from semi-batch and batch operations are compared. Processing takes longer in the semi-batch operations and complete conversions are only practical in this mode when enzyme is added to substrate.     

Some experimental findings in compression-after-impact (CAI) tests of CF/PEEK (APC-2) and conventional CF/epoxy flat plates

Compression-after-impact (CAI) tests have been conducted for quasi-isotropic thick plates with 48 plies by using the NASA method and on plates with 32 plies by using the SACMA method. Specimens are made of CF/PEEK (APC-2) and conventional CF/epoxy for the NASA plates and CF/epoxy for the SACMA plates. In the NASA CAI tests, the sequence of delamination buckling and its propagation is clearly revealed through various experimental techniques. One major technique is moiré topography, and the other is thermo-mechanical stress analysis with a high-accuracy infrared sensor. The arrest of delamination propagation just before catastrophic failure due to high fracture toughness is clearly captured by the moiré camera. This behavior provides good CAI values of CF/PEEK. The initial buckling properties of the delaminated region by the impact are then extensively discussed. Numerical predictions of initial buckling stress have been obtained by modelled geometry of the delaminated region simplified from its precise structure clarified by ultrasonic C-scanning. They agree fairly well with the experimental results. The in-plane stress distribution in the delaminated region before initial buckling is measured by an infrared stress graphic system. This compared favorably with finite element predictions. Two types of symmetric buckling modes with respect to the central plate surface, twin and single peak ones, are experimentally captured.     

The determinants of heat-shock element-directed lacZ expression in Saccharomyces cerevisiae.

Heat-shock induction of heat-shock protein genes is due to a specific promoter element (the heat-shock element, HSE). This study used lacZ under HSE control (HSE-lacZ) to characterize HSE activity in Saccharomyces cerevisiae cells of different physiological states and differing genetic backgrounds. In batch fermentations HSE-lacZ induction by heat shock was maximal in exponential growth, and showed marked decline with the approach to stationary phase. Expression in the absence of heat shock was unaffected by growth phase, indicating that the growth-dependent expression of many yeast heat-shock genes uses promoter elements in addition to the HSE. Heat-induced expression was strongly influenced by the temperature at which cultures were grown. While basal, uninduced expression was constant during growth at different temperatures to 30 degrees C, induction by transfer to 39 degrees C was reduced by increases in growth temperature as low as 18-24 degrees C. Maximal HSE-lacZ induction (30- to 50-fold) was in cultures grown at low temperatures (18-24 degrees C), then heat shocked at 39 degrees C. Ethanol was a poor inducer. Mutations having little effect on HSE-lacZ expression included a respiratory petite; ubi4 (which inactivates the poly-ubiquitin gene); also ubc4 and ubc5 (which each inactivate one of the ubiquitin ligases involved in degradation of aberrant protein). pep4-3 increased both basal and induced beta-galactosidase about two-fold, probably because of slower turnover of this enzyme in pep4-3 strains.