Adsorption of block copolymers at latex surface and their utilization in emulsion polymerization

Amphiphilic block copolymers have been investigated for their utilization in emulsion polymerization of butyl methacrylate. Special attention has been paid to the adsorption mechanism of the block copolymers from systematic measurements of equilibrium adsorption isotherms. A series of well-defined water-soluble amphiphilic block copolymers, composed of poly(butyl methacrylate) and poly(sodium methacrylate) blocks, were synthesized by anionic polymerization of butyl methacrylate and tert-butyl methacrylate followed by the thermal deprotection of the tert-butyl ester groups and final hydrolysis. The number density of emulsion polymer particles N_P varied as [copolymer]^α, α lying between 0.44 and 0.73 according to the hydrophilic content of the copolymers. In contrast with SDS taken as a reference emulsifier, the adsorption of the copolymers was very strong and this provided quite an efficient stabilization of the polymer particles during emulsion polymerization, even at low concentrations (<10⁻⁴ mol L⁻¹) and low coverages (<10% of the interfacial area).     

Preparation of optically active poly β-propiolactones

Racemic -methyl--n-propyl--propiolactone is readily polymerized with zinc and cadmium chiral glycolates leading to optically active polyesters. The stereoelectivities observed are lower than for oxiranes and thiiranes with the same initiator system. A value of rotatory power for pure enantiomer _o, is deduced from NMR measurements in the presence of chiral solvent. The structure of polymers is discussed on the basis of NMR results.     

Polyunsaturated fatty acids in tissues of rats fed trielaidin and high or low levels of linolenic acid

Male and female weanling rats that were born to dams fed a diet low in linolenic acid received diets of 15% lipids by weight containing 45% elaidic acid (as trielaidin) and 8.5% or 0.1% linolenic acid for 10 weeks. Four other groups, in which palmitic or oleic acid replaced elaidic acid in the diet, served as controls. The fatty acid profiles of several lipid classes were determined in adipose tissue, adrenals, testes, heart and brain. Elaidic acid was incorporated into tissue lipids in varying degrees, depending on the organ and on the lipid class. Feeding elaidic acid induced no changes in the polyunsaturated fatty acid (PUFA) profiles of testes lipids but resulted in definite modifications of the PUFA patterns of heart phosphatidylcholine (PC) and phosphatidylethanolamine (PE). In linolenic acid-deprived rats, arachidonic acid was decreased in PC and linoleic acid was increased in both PC and PE; 22∶5n−6 was strongly depressed in both PC and PE. In linolenic acid-fed rats, 22∶6n−3 was decreased in PC and PE. These changes, on the whole, were more evident in females, and some also were observed in adrenal cholesteryl esters but only slightly in brain phospholipids. the apparent inhibition of the biosynthesis of PUFA induced by dietary elaidic acid appeared to be complex and of greater intensity in the n−6 fatty acid series than in their n−3 homologues.     

3He impurities on the bulk surface of liquid4He: Possible existence of excited states

We study, using a density-functional approach, the properties of the two-dimensional system formed by³He atoms on the surface of liquid⁴He, as a function of³He coverageN _s , at zero temperature. We find several types of surface states accessible to the³He atoms. For small values ofN _s , the surface tension is, as expected, linear inN _s ² . For a coverage of about half a monolayer, a new type of surface state starts being occupied, and this produces a change in the slope of as a function ofN _s ² and, more clearly, a step in the surface specific heat, which increases by a factor of almost two. Another step is predicted to occur for a coverage of 1.3 monolayer. Existing data are compatible with this structure of surface states but are not numerous enough to prove or disprove the existence of steps.Unité de Recherche des Universités Paris 11 et Paris 6 Associée au CNRS.     

Dynamic Model Adaptation for Multiscale Simulation of Hyperbolic Systems with Relaxation

In numerous industrial CFD applications, it is usual to use two (or more) different codes to solve a physical phenomenon: where the flow is a priori assumed to have a simple behavior, a code based on a coarse model is applied, while a code based on a fine model is used elsewhere. This leads to a complex coupling problem with fixed interfaces. The aim of the present work is to provide a numerical indicator to optimize to position of these coupling interfaces. In other words, thanks to this numerical indicator, one could verify if the use of the coarser model and of the resulting coupling does not introduce spurious effects. In order to validate this indicator, we use it in a dynamical multiscale method with moving coupling interfaces. The principle of this method is to use as much as possible a coarse model instead of the fine model in the computational domain, in order to obtain an accuracy which is comparable with the one provided by the fine model. We focus here on general hyperbolic systems with stiff relaxation source terms together with the corresponding hyperbolic equilibrium systems. Using a numerical Chapman–Enskog expansion and the distance to the equilibrium manifold, we construct the numerical indicator. Based on several works on the coupling of different hyperbolic models, an original numerical method of dynamic model adaptation is proposed. We prove that this multiscale method preserves invariant domains and that the entropy of the numerical solution decreases with respect to time. The reliability of the adaptation procedure is assessed on various 1D and 2D test cases coming from two-phase flow modeling.     

Binarised regression tasks: methods and evaluation metrics

Some supervised tasks are presented with a numerical output but decisions have to be made in a discrete, binarised, way, according to a particular cutoff. This binarised regression task is a very common situation that requires its own analysis, different from regression and classification—and ordinal regression. We first investigate the application cases in terms of the information about the distribution and range of the cutoffs and distinguish six possible scenarios, some of which are more common than others. Next, we study two basic approaches: the retraining approach, which discretises the training set whenever the cutoff is available and learns a new classifier from it, and the reframing approach, which learns a regression model and sets the cutoff when this is available during deployment. In order to assess the binarised regression task, we introduce context plots featuring error against cutoff. Two special cases are of interest, the \( UCE \) and \( OCE \) curves, showing that the area under the former is the mean absolute error and the latter is a new metric that is in between a ranking measure and a residual-based measure. A comprehensive evaluation of the retraining and reframing approaches is performed using a repository of binarised regression problems created on purpose, concluding that no method is clearly better than the other, except when the size of the training data is small.     

Fuzzy fault tolerant predictive control for a diesel engine air path

This paper proposes a Fuzzy Fault Tolerant Predictive Control (FFTPC) with integral action method for a class of nonlinear systems. The Takagi-Sugeno (T-S) fuzzy approach is introduced as a modelling technique in order to consider the active control methods adapted to linear models. The proposed control strategy is based on a combination between Parallel Distributed Compensation (PDC) control law and Model Predictive Control (MPC) where the T-S fuzzy aspect uses the Unmeasurable Premise Variables (UPV). A T-S fuzzy observer provides an L2 norm estimation of system state vector and faults. The controller and observer gains are obtained by solving Linear Matrix Inequalities (LMIs) derived from the Lyapunov theory. The validity of the proposed Fault Tolerant Control (FTC) strategy is illustrated through an application to a Diesel Engine Air Path (DEAP) system.