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.     

Motional heterogeneity of polystyrene-block-polybutadiene: a spin probe study

Polystyrene-block-polybutadiene copolymers (SB) with 0.5 mass fraction of styrene were studied by electron spin resonance (ESR) of nitroxide spin probes. The influence of the block length ( and ) and the solvation power of casting solvents on the motional dynamics of spin probe were measured over a wide temperature range. Two nitroxide radicals as spin probes were selected: 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl benzoate (BzONO) and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (Tempol). Irrespective of the spin probe used two ESR spectral components differing in their motional properties above the phase transition of polybutadiene blocks (PB) were observed. The fast component was assigned to spin probes located in polybutadiene-rich domains and the slow component to spin probes in polystyrene-rich domains. The range of two spectral components and the phase transition of the slow ESR component, T_5mT, depend on the block length. The influence of the interphase and accumulation of free volume in the interphase on the Tempol probe motion was investigated by changing copolymer morphology in the films casted from selective and nonselective solvents. The analysis of the motional heterogeneity from the ratio of the fast and slow motional component presents evidence that in the selective solvent for polystyrene (PS) blocks (2-butanone) the most irregular structure with a large interphase is formed. The difference in fast motion of spin probes indicates that the motional dynamic is related to the change of domain structure.     

Interaction between dietary protein and fat in triglyceride metabolism in the rat: Effects of soy protein and menhaden oil

The objective of the present study was to determine the mechanisms by which dietary proteins interact with dietary lipids in the regulation of triglyceridemia in rats. Male Sprague-Dawley rats (n=56) were subjected to 28-d experimental diets containing different combinations of proteins (20% w/w) and lipid sources (14% w/w): (i) casein-menhaden oil, (ii) casein-beef tallow, (iii) soy protein-menhaden oil, and (iv) soy protein-beef tallow. Significant protein-lipid interactions were observed on triglyceridemia and hepatic cholesterol in fasted rats. The combination of casein and beef tallow was associated with high plasma TG and hepatic cholesterol concentrations, which were reduced by substitution either of soy for casein or of menhaden oil for beef tallow. Therefore, triglyceridemia and liver cholesterol remained low with soy protein feeding, independently of the lipid source, as well as with menhaden oil feeding, regardless of the protein source. The menhaden oil diets reduced plasma cholesterol, hepatic TG, and TG secretion compared with beef tallow diets independently of the dietary protein source. Modifying the source of dietary proteins and lipids had no effect on post-heparin plasma lipoprotein lipase activity. These results demonstrate that soy protein can lower rat triglyceridemia relative to casein when associated with beef tallow consumption, whereas menhaden oil can attenuate hypertriglyceridemia when rats are fed casein. The data further suggest that part of the hypotriglyceridemic effect of soy protein in the rat may be mediated by reduced hepatic lipid synthesis, as is the case for menhaden oil.     

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.     

Air impingement and intermittent drying: Application to apple and to mango

An original drying process combining air impingement and intermittent drying was studied on apple slices and mango cubes. The influence of four operating parameters (air velocity, drying/tempering periods, upper height, and air temperature) on the drying time and on the drying rate was evaluated. Continuous and intermittent drying were compared. The intermittency α = 1/7 (τ_on = 10 seconds and τ_off = 60 seconds) gave the best results. A time savings of 54% for apple and 67% for mango was reached. In continuous drying, a time savings of 4620 seconds was observed by increasing the air velocity from 6 to 40 m s^?1 for apple. Air temperatures of 328 K for apple and of 328 K or 338 K for mango were determined as optimum to prevent case‐hardening. Experimental results were fitted with the analytical solution of Fick's second law and the modified Page equation (average values R² = 0.985 and 0.961, for apple and mango, respectively). For both products, the apparent moisture diffusivity D_app, the drying constant k, the drying coefficient n, and the activation energy E_a, were identified. Activation energies calculated from the analytical solution were 30.3 and 36.8 kJ mol^?1 and were 25.4 and 30.0 kJ mol^?1 using the modified Page equation for apple and mango, respectively. Mango has an increased temperature sensitivity and thus will need less energy for drying than apple.     

Detection and evaluation of the fibers' deposition parameters during wet filament winding

Wet filament winding technology has been extensively used for the manufacture of rotationally symmetric parts made of fiber-reinforced plastics (FRP). As the design and modeling of FRP-parts require numerous assumptions, deviations between calculated and achieved mechanical properties are expected. One aspect that contributes to this discrepancy is the assumption of a homogeneous rectangular cross-section of the fiber-band. In this work, the fiber-band geometry in a wet-winding process of carbon fiber cylinders is analyzed. An Infrared-optical system for the detection of the fiber bandwidth and winding-angle is implemented. The influence of the winding speed and the resin temperature is analyzed. An image processing algorithm for the automatic measurement of the fiber's bandwidth and winding-angle is developed. Manual and adaptive gamma corrections are implemented to improve image quality. A parameter study for the suitable selection of image processing parameters is performed.     

3D MRI of explanted sheep hearts with submillimeter isotropic spatial resolution: comparison between diffusion tensor and structure tensor imaging

Magnetic Resonance Materials in Physics, Biology and Medicine - The aim of the study is to&nbsp;compare structure tensor imaging (STI) with diffusion tensor imaging (DTI) of the sheep heart...     

NH_3 Plasma Surface Treatments of Engineering Fluoropolymers: A Way to Enhance Adhesion of Ni or Cu Thin Films Deposited by Electroless Plating

FLUOROPOLYMERS(FPs)are thermoplasticmaterials which exhibit a number of unique chemicaland physical characteristics that no other man-madeplastic product gets together.For example,FPs showvery good resistance to almost all chemicals,excellentwater vapor barrier properties,high thermal stability,outstanding electrical insulation properties(lowdielectric constant and dissipation factors),extremelylow frictional coefficient giving them high auto-lubrication properties,high resistance to rad…     

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.