Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007     

Semi-implicit complementary volume scheme for solving level set like equations in image processing and curve evolution

Summary. We introduce linear semi-implicit complementary volume numerical scheme for solving level set like nonlinear degenerate diffusion equations arising in image processing and curve evolution problems. We study discretization of image selective smoothing equation of mean curvature flow type given by Alvarez, Lions and Morel ([3]). Solution of the level set equation of Osher and Sethian ([26], \[30]) is also included in the study. We prove and estimates for the proposed scheme and give existence of its (generalized) solution in every discrete time-scale step. Efficiency of the scheme is given by its linearity and stability. Preconditioned iterative solvers are used for computing arising linear systems. We present computational results related to image processing and plane curve evolution. Received April 25, 2000 / Revised version received June 11, 2001 / Published online November 15, 2001     

Continuous modified Newton’s-type method for nonlinear operator equations

A nonlinear operator equation F(x)=0, F:H→H, in a Hilbert space is considered. Continuous Newton’s-type procedures based on a construction of a dynamical system with the trajectory starting at some initial point x ₀ and becoming asymptotically close to a solution of F(x)=0 as t→+∞ are discussed. Well-posed and ill-posed problems are investigated. Received: June 29, 2001; in final form: February 26, 2002?Published online: February 20, 2003 This paper was finished when AGR was visiting Institute for Theoretical Physics, University of Giessen. The author thanks DAAD for support     

Runge–Kutta convolution quadrature methods for well-posed equations with memory

Runge–Kutta based convolution quadrature methods for abstract, well-posed, linear, and homogeneous Volterra equations, non necessarily of sectorial type, are developed. A general representation of the numerical solution in terms of the continuous one is given. The error and stability analysis is based on this representation, which, for the particular case of the backward Euler method, also shows that the numerical solution inherits some interesting qualitative properties, such as positivity, of the exact solution. Numerical illustrations are provided.     

Completely empty pyramids on integer lattices and two-dimensional faces of multidimensional continued fractions

In this paper we develop an integer-affine classification of three-dimensional multistory, completely empty convex marked pyramids. We apply it to obtain the complete lists of compact two-dimensional faces of multidimensional continued fractions lying in planes at integer distances 2, 3, 4, …  to the origin. The faces are considered up to the action of the group of integer-linear transformations.     

Equivariant fixed-point indices of iterated maps

We describe an equivariant version (for actions of a finite group G) of Dold’s index theory, [10], for iterated maps. Equivariant Dold indices are defined, in general, for a G-map U → X defined on an open G-subset of a G-ANR X (and satisfying a suitable compactness condition). A local index for isolated fixed-points is introduced, and the theorem of Shub and Sullivan on the vanishing of all but finitely many Dold indices for a continuously differentiable map is extended to the equivariant case. Homotopy Dold indices, arising from the equivariant Reidemeister trace, are also considered.      

A fictitious domain approach to the numerical solution of PDEs in stochastic domains

We present an efficient method for the numerical realization of elliptic PDEs in domains depending on random variables. Domains are bounded, and have finite fluctuations. The key feature is the combination of a fictitious domain approach and a polynomial chaos expansion. The PDE is solved in a larger, fixed domain (the fictitious domain), with the original boundary condition enforced via a Lagrange multiplier acting on a random manifold inside the new domain. A (generalized) Wiener expansion is invoked to convert such a stochastic problem into a deterministic one, depending on an extra set of real variables (the stochastic variables). Discretization is accomplished by standard mixed finite elements in the physical variables and a Galerkin projection method with numerical integration (which coincides with a collocation scheme) in the stochastic variables. A stability and convergence analysis of the method, as well as numerical results, are provided. The convergence is “spectral” in the polynomial chaos order, in any subdomain which does not contain the random boundaries.     

A p-version finite element method for nonlinear elliptic variational inequalities in 2D

This article introduces and analyzes a p-version FEM for variational inequalities resulting from obstacle problems for some quasi-linear elliptic partial differential operators. We approximate the solution by controlling the obstacle condition in images of the Gauss–Lobatto points. We show existence and uniqueness for the discrete solution u _p from the p-version for the obstacle problem. We prove the convergence of u _p towards the solution with respect to the energy norm, and assuming some additional regularity for the solution we derive an a priori error estimate. In numerical experiments the p-version turns out to be superior to the h-version concerning the convergence rate and the number of unknowns needed to achieve a certain exactness of the approximation.     

Primes in quadratic progressions on average

In this paper, we establish a theorem on the distribution of primes in quadratic progressions on average.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007