Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

Sensitivity of trust-region algorithms to their parameters

In this paper, we examine the sensitivity of trust-region algorithms on the parameters related to the step acceptance and update of the trust region. We show, in the context of unconstrained programming, that the numerical efficiency of these algorithms can easily be improved by choosing appropriate parameters. Recommended ranges of values for these parameters are exhibited on the basis of extensive numerical tests. MSC classification: 65K05, 90C26, 90C30     

厅堂音质评价参量的相关性分析

当代室内声学专家经常选用的评价厅堂音质的物理参量，其间有几个量是相关的。作为室内音质设计的依据．必须寻找基本相互独立的参量，才有更大的实用意义。     

Reducing system of parameters and the Cohen-Macaulay property

Let R be a local ring and let (x ₁, …, x _r) be part of a system of parameters of a finitely generated R-module M, where r < dim_R M. We will show that if (y ₁, …, y _r) is part of a reducing system of parameters of M with (y ₁, …, y _r) M = (x ₁, …, x _r) M then (x ₁, …, x _r) is already reducing. Moreover, there is such a part of a reducing system of parameters of M iff for all primes P ε Supp M ∩ V _R(x ₁, …, x _r) with dim_R R/P = dim_R M − r the localization M _P of M at P is an r-dimensional Cohen-Macaulay module over R _P. Furthermore, we will show that M is a Cohen-Macaulay module iff y _d is a non zero divisor on M/(y ₁, …, y _d−1) M, where (y ₁, …, y _d) is a reducing system of parameters of M (d:= dim_R M).     

Boundary-Value Problem of Drainage in a Fresh Groundwater Fringe above Saline Groundwater

A multiparameter boundary-value problem of fresh infiltration water seepage in a drained fringe above quiescent saline water is solved in the direct statement and studied in detail.     

Guaranteed-accuracy approximation of reachable sets for a linear dynamic system subject to impulse actions

A method is proposed for approximating the reachable set of a dynamic system with a state space dimension no higher than six-eight considered on a finite time interval. The system is governed by linear differential equations with piecewise constant coefficients and impulse actions specified at prescribed times. The method is based on guaranteed-accuracy polyhedral approximations of reachable sets at researcher-specified times. Every approximation is constructed using the preceding one. A procedure is described for choosing parameters of the method that ensure the required accuracy with close-to-minimal time costs.     

Characterization of semiconductor laser frequency chirp based on signal distortion in dispersive optical fiber

In the paper, the simple method of laser chirp parameters estimation is presented. It is based on measuring time-domain distortions of chirped signal transmitted through dispersive fiber and finding laser chirp parameters by matching measured distortions to calculated ones. Experiments undertaken with 1.55 μm telecommunication grade distributed feedback (DFB) lasers and standard single-mode fiber are described, together with some practical remarks on measurement setup and main conclusions.     

Reliable evaluation of temperature-independent parameters in correlation of vapour–liquid equilibrium data

A new algorithm/program has been elaborated for simultaneous processing of different sets of vapour–liquid equilibrium data. The program was tested with six binary hexane + isomeric pentanol systems, each of them measured at three different isobaric conditions and one isothermal system of tert-butyl-methyl-ether + 2-methyl-2-propanol measured at three different temperatures. The correlation uses the maximum likelihood method, taking into account real behaviour of vapour phase. The parameters obtained are valid within the whole temperature range of the data, and are consistent in comparison with those obtained from individual correlations of isobars or isotherms. Results are presented for the Wilson and NRTL equations.     

pH,Definition and measurement at high temperatures

In this review paper, the NBS scale and its limitations are briefly discussed. The magnitude of liquid junction potentials and some calculated values are presented. The use of a molality scale for hydrogen electrode concentration cells at high temperatures is described, and results from measurements on ionization equilibria are summarized. Use of this scale is also recommended for certain circumstances with cells without liquid junction. As an alternative activity scale, use of the Pitzer ion-interaction treatment for ions is recommended for special cases. Finally, reference data are presented for _±HCl in HCl(aq) to 350°C and (HCl+NaCl)(aq) to 200°C that were derived by use of the Pitzer ion-interaction treatment.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.