Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Sur les racines de certaines équations

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Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

On the Physical Origin of Long-Ranged Fluctuations in Fluids in Thermal Nonequilibrium States

Thermodynamic fluctuations in systems that are in nonequilibrium steady states are always spatially long ranged, in contrast to fluctuations in thermodynamic equilibrium. In the present paper we consider a fluid subjected to a stationary temperature gradient. Two different physical mechanisms have been identified by which the temperature gradient causes long-ranged fluctuations. One cause is the presence of couplings between fluctuating fields. Secondly, spatial variation of the strength of random forces, resulting from the local version of the fluctuation-dissipation theorem, has also been shown to generate long-ranged fluctuations. We evaluate the contributions to the long-ranged temperature fluctuations due to both mechanisms. While the inhomogeneously correlated Langevin noise does lead to long-ranged fluctuations, in practice, they turn out to be negligible as compared to nonequilibrium temperature fluctuations resulting from the coupling between temperature and velocity fluctuations.     

On Hyperbolic Variational Inequalities of First Order and Some Applications

This paper presents further developments in the study of strong solutions and their coincidence sets to the obstacle problem for linear transport operators. Under natural mild assumptions, the strong convergence of the solutions and the characteristic functions of their coincidence sets is obtained in the passage of second order to first order problems. An application to a steady-state chemotaxis problem is given. The extension to the two obstacles problem of first order is also presented, having in view an application to a porous media model in presence of saturation arising in petroleum engineering.     

The linear polarization constant of R n

Summary He present work deals with estimations of the n-th linear polarization constant c(H)_n of an n-dimensional real Hilbert space H. We provide some new lower bounds on the value of sup_║y║=1 │1,y> ... n,y>│, where x₁, ... ,x_n are unit vectors in H. In particular, the results improve an earlier estimate of Marcus. However, the intriguing conjecture c(H) _n= n^n/2 remains open.     

Analysis of semiconducting materials by high-resolution radiofrequency glow discharge mass spectrometry

The analytical capabilities of a high-resolution mass spectrometer in combination with a 13.56 MHz glow discharge ion source for the analysis of semiconducting materials (silicon carbide and gallium arsenide) were studied. It was shown that single positively charged ions of sample material have about 10 eV higher average energy than the ions of the discharge and residual gas. Therefore effective energy separation of the ions of analyte from the ions of the discharge and residual gas was achieved by adjusting the ion transfer optics (breadth and position of energy slit), which improves the analytical capabilities of the developed method.Some analytical applications are presented to illustrate the performance of r.f. GDMS for the bulk analysis of semiconducting materials. The results of the trace element analysis of gallium arsenide and silicon carbide samples are compared with data of independent methods (LIMS, ICP-AES, SIMS).Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthdayOn leave from the Institute of Inorganic Chemistry, 630090 Novosibirsk, Russia     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

Champ de vitesse dans un échangeur à vortex en régime turbulentHeat exchanger velocity field with turbulent inlet condition

We consider the isothermal flow through a cylindrical flat chamber, a model of some particular heat exchanger, for which LDV measurements and a numerical simulation have been performed. Experimental results show the establishment of an important vortex zone, the secondary flow extending all along the chamber radius. This observation leads to an expected significant increase of the fluid mixing. Results issued from the numerical simulation appear to be in close agreement with experimental data. Nevertheless, the k–ε model used here must be improved to obtain a better approach near the vortex centre. To cite this article: S. Petitot et al., C. R. Mecanique 330 (2002) 593–599.     

Acetylene weak bands at 2.5 μm from intracavity Cr:ZnSe laser absorption observed with time-resolved Fourier transform spectroscopy

The spectral dynamics of a mid-infrared multimode Cr(2+):ZnSe laser located in a vacuum sealed chamber containing acetylene at low pressure is analyzed by a stepping-mode high-resolution time-resolved Fourier transform interferometer. Doppler-limited absorption spectra of C(2)H(2) in natural isotopic abundance are recorded around 4000 cm(-1) with kilometric absorption path lengths and sensitivities better than 3 10(-8) cm(-1). Two cold bands are newly identified and assigned to the ν(1)+ν(4) (1) and ν(3)+ν(5) (1) transitions of (12)C(13)CH(2). The ν(1)+ν(5) (1) band of (12)C(2)HD and fourteen (12)C(2)H(2) bands are observed, among which for the first time ν(2)+2ν(4) (2)+ν(5) (-1).