Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

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     

Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

Control of a liquid–liquid heat exchanger

 The analytical solutions of equations describing the dynamics of distributed parameter systems are usually complicated in form and derivations and inconvenient to use for simulation and control system design. The liquid–liquid counter flow heat exchanger is an example of these disturbed parameter systems. An analytical solution of the dynamics of a symmetrically operated counter flow heat exchanger in the form of transfer function matrix is investigated in open-loop and close-loop conditions. The resulting non-linear model was linearized using perturbation approach. A feed-forward path controller to counteract at any disturbances in the boundary temperature and a non-interactive controller to decouple the outputs were implemented. Received on 22 February 2001 / Published online: 29 November 2001     

Needle Variations and Almost Lower Semicontinuous Differential Inclusions

It is shown that the construction of needle variations can be carried out for almost lower semicontinuous differential inclusions rather than for the case of ordinary single-valued continuously differentiable vector fields usually considered in the literature. The construction leads to needle variations whose flows are in general set-valued but still have good differentiability properties. The variations are constructed by using single-valued selections that are not necessarily continuous with respect to the state variable, but have instead a much weaker 'integral continuity' property, somewhat more general that the 'directional continuity' considered in previous work by A. Cambini and S. Querci, A. Pucci, and A. Bressan. The existence of many such selections is proved by slightly adapting an argument due to Bressan, extending it from the lower semicontinuous to the almost lower semicontinuous case, and strengthening it to yield not only directional continuity at all points but also full continuity at a specified point.     

Unified approach to best unbiased estimation in control problems and linear models

An analog of a sufficient statistic is proposed in the finite-dimensional linear space of statistics. It is shown that the unbiased estimator of the linear function of a parameter closest to a given function, expressed in terms of a minimal linearly sufficient statistic, is potentially unbiased and optimal.Translated from Statisticheskie Metody Otsenivaniya i Proverki Gipotez, pp. 51–58, 1986.     

Asymptotic integration of a problem of convection

Rostov-on-Don. Translated from Sibirskii Matematicheskii Zhurnal, Vol. 30, No. 4, pp. 69–75, July–August, 1989.     

Self-broadening in the millimeter-wave spectrum of ozone

Self broadened widths of seven lines of ozone between 75 and 120 GHz have been measured at room temperature. The variation with temperature of the self-broadening parameter for three of these lines has been studied in the range 245–292°K.