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  • 1
    Publication Date: 2014-02-26
    Description: Manufacturing is a topic that provides rich opportunities for important mathematical contributions to real-world problems. The purpose of this paper is to show, by means of several examples, where and how mathematical problems of a discrete nature arise in manufacturing and to demonstrate the savings and improvements that can be achieved by employing the techniques of combinatorial optimization. The topics covered range from the design phase of a product (e. g.,routing, placement and via minimization in VLSI design), the control of CNC machines (e. g., drilling and plotting), to the management of assembly lines, storage systems and whole factories. We also point out difficulties in the modelling of complex situations and outline the algorithmic methods that are used for the solution of the mathematical problems arising in manufacturing. {\bf Key words:} discrete mathematics , combinatorial optimization, applications to manufacturing.
    Keywords: ddc:000
    Language: English
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  • 2
    Publication Date: 2014-02-26
    Description: Large scale combustion simulations show the need for adaptive methods. First, to save computation time and mainly to resolve local and instationary phenomena. In contrast to the widespread method of lines, we look at the reaction- diffusion equations as an abstract Cauchy problem in an appropriate Hilbert space. This means, we first discretize in time, assuming the space problems solved up to a prescribed tolerance. So, we are able to control the space and time error separately in an adaptive approach. The time discretization is done by several adaptive Runge-Kutta methods whereas for the space discretization a finite element method is used. The different behaviour of the proposed approaches are demonstrated on many fundamental examples from ecology, flame propagation, electrodynamics and combustion theory. {\bf Keywords:} initial boundary value problem, Rothe- method, adaptive Runge-Kutta method, finite elements, mesh refinement. {\bf AMS CLASSIFICATION:} 65J15, 65M30, 65M50.
    Keywords: ddc:000
    Language: English
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  • 3
    Publication Date: 2014-02-26
    Description: In this paper we describe a cutting plane algorithm for the Steiner tree packing problem. We use our algorithm to solve some switchbox routing problems of VLSI-design and report on our computational experience. This includes a brief discussion of separation algorithms, a new LP-based primal heuristic and implementation details. The paper is based on the polyhedral theory for the Steiner tree packing polyhedron developed in our companion paper SC 92-8 and meant to turn this theory into an algorithmic tool for the solution of practical problems.
    Keywords: ddc:000
    Language: English
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  • 4
    Publication Date: 2014-02-26
    Description: Let $G=(V,E)$ be a graph and $T\subseteq V$ be a node set. We call an edge set $S$ a Steiner tree with respect to $T$ if $S$ connects all pairs of nodes in $T$. In this paper we address the following problem, which we call the weighted Steiner tree packing problem. Given a graph $G=(V,E)$ with edge weights $w_e$, edge capacities $c_e, e \in E,$ and node sets $T_1,\ldots,T_N$, find edge sets $S_1,\ldots,S_N$ such that each $S_k$ is a Steiner tree with respect to $T_k$, at most $c_e$ of these edge sets use edge $e$ for each $e\in E$, and such that the sum of the weights of the edge sets is minimal. Our motivation for studying this problem arises from the routing problem in VLSI-design, where given sets of points have to be connected by wires. We consider the Steiner tree packing Problem from a polyhedral point of view and define an appropriate polyhedron, called the Steiner tree packing polyhedron. The goal of this paper is to (partially) describe this polyhedron by means of inequalities. It turns out that, under mild assumptions, each inequality that defines a facet for the (single) Steiner tree polyhedron can be lifted to a facet-defining inequality for the Steiner tree packing polyhedron. The main emphasis of this paper lies on the presentation of so-called joint inequalities that are valid and facet-defining for this polyhedron. Inequalities of this kind involve at least two Steiner trees. The classes of inequalities we have found form the basis of a branch & cut algorithm. This algorithm is described in our companion paper SC 92-09.
    Keywords: ddc:000
    Language: English
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  • 5
    Publication Date: 2020-10-05
    Description: The placement in the layout design of electronic circiuts consists of finding a non- overlapping assignment of rectangular cells to positions on the chip so what wireability is guaranteed and certain technical constraints are met.This problem can be modelled as a quadratic 0/1- program subject to linear constraints. We will present a decomposition approach to the placement problem and give results about $NP$-hardness and the existence of $\varepsilon$-approximative algorithms for the involved optimization problems. A graphtheoretic formulation of these problems will enable us to develop approximative algorithms. Finally we will present details of the implementation of our approach and compare it to industrial state of the art placement routines. {\bf Keywords:} Quadratic 0/1 optimization, Computational Complexity, VLSI-Design.
    Keywords: ddc:000
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  • 6
    Publication Date: 2014-02-26
    Description: Dieses Paper enthält die ersten beiden Teile einer geplanten Serie von Aufsätzen über die $CPLEX^2$-Implementierung des Simplex- Verfahrens. Der erste Teil ist eine Einführung: er liefert eine kurze Beschreibung des Verfahrens für Probleme mit beschränkten Variablen, zusammen mit einer relativ ausführlichen Diskussion der numerischen Eigenschaften der Netlib-Probleme. Diese Probleme bilden auch das Fundament der rechnerischen Untersuchungen in den folgenden Teilen. Der zweite Teil enthält die Hauptergebnisse dieses Papers, eine Beschreibung der Methode, die von CPLEX verwendet wird, um eine Startbasis zu konstruieren.
    Keywords: ddc:000
    Language: German
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  • 7
    Publication Date: 2014-02-26
    Description: Models for occupation dynamics in discrete quantum systems lead to large or even infinite systems of ordinary differential equations. Some new mathematical techniques, developed for the simulation of chemical processes, make a numerical solution of countable systems of ordinary differential equations possible. Both, a basic physical concept for the construction of such systems and the structure of the numerical tools for solving them are presented. These conceptual aspects are illustrated by a simulation of an occupation process from spectroscopy. In this example the structures of rotation spectra observed in infrared spectroscopy are explained and some possibilities for an extension of the model are shown.
    Keywords: ddc:000
    Language: English
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  • 8
    Publication Date: 2020-12-14
    Description: We present a polyhedral approach for the general problem of designing a minimum-cost network with specified connectivity requir
    Keywords: ddc:000
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  • 9
    Publication Date: 2014-02-26
    Description: In two-parameter systems two symmetry breaking bifurcation points of different types coalesce generically within one point. This causes secondary bifurcation points to exist. The aim of this paper is to understand this phenomenon with group theory and the innerconnectivity of irreducible representations of supergroup and subgroups. Colored pictures of examples are included.
    Keywords: ddc:000
    Language: English
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  • 10
    Publication Date: 2014-02-26
    Description: In this paper we investigate separation problems for classes of inequalities valid for the polytope associated with the Steiner tree packing problem, a problem that arises, e.~g., in VLSI routing. The separation problem for Steiner partition inequalities is ${\cal N}\hskip-2pt{\cal P}$-hard in general. We show that it can be solved in polynomial time for those instances that come up in switchbox routing. Our algorithm uses dynamic programming techniques. These techniques are also applied to the much more complicated separation problem for alternating cycle inequalities. In this case we can compute in polynomial time, given some point $y$, a lower bound for the gap $\alpha-a^Ty$ over all alternating cycle inequalities $a^Tx\ge\alpha$. This gives rise to a very effective separation heuristic. A by-product of our algorithm is the solution of a combinatorial optimization problem that is interesting in its own right: Find a shortest path in a graph where the ``length'' of a path is its usual length minus the length of its longest edge.
    Keywords: ddc:000
    Language: English
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  • 11
    Publication Date: 2014-02-27
    Description: Gegeben sei ein Graph $G=(V,E)$ mit positiven Kantenkapazitäten $c_e$ und Knotenmengen $T_1,\ldots,T_N$. Das Steinerbaumpackungs-Problem besteht darin, Kantenmengen $S_1,\ldots,S_N$ zu finden, so da\ss\ jedes $S_k$ die Knoten aus $T_k$ verbindet und jede Kante $e$ in höchstens $c_e$ Kantenmengen aus $S_1,\ldots,S_N$ vorkommt. Eine zulässige Lösung dieses Problems nennen wir eine Steinerbaumpackung. Ist zusätzlich eine Gewichtung der Kanten gegeben und nach einer bezüglich dieser Gewichtung minimalen Steinerbaumpackung gesucht, so sprechen wir vom gewichteten Steinerbaumpackungs-Problem. Die Motivation zum Studium dieses Problems kommt aus dem Entwurf elektronischer Schaltungen. Ein dort auftretendes Teilproblem ist das sogenannte Verdrahtungsproblem, das im wesentlichen darin besteht, gegebene Punktmengen unter bestimmten Nebenbedingungen und Optimalitätskriterien auf einer Grundfläche zu verbinden. Wir studieren das Steinerbaumpackungs-Problem aus polyedrischer Sicht und definieren ein Polyeder, dessen Ecken genau den Steinerbaumpackungen entsprechen. Anschlie\ss end versuchen wir, dieses Polyeder durch gute'' beziehungsweise facetten-definierenden Ungleichungen zu beschreiben. Basierend auf diesen Ungleichungen entwickeln wir ein Schnittebenenverfahren. Die Lösung des Schnittebenenverfahrens liefert eine untere Schranke für die Optimallösung und dient als Grundlage für die Entwicklung guter Primalheuristiken. Wir haben das von uns implementierte Schnittebenenverfahren an einem Spezialfall des Verdrahtungsproblems, dem sogenannten Switchbox-Verdrahtungsproblem, getestet und vielversprechende Ergebnisse erzielt.
    Keywords: ddc:000
    Language: German
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 12
    Publication Date: 2014-02-26
    Description: The numerical treatment of Equivariant parameter-dependent onlinear equation systems, and even more its automation requires the intensive use of group theory. This paper illustrates the group theoretic computations which are done in the preparation of the numerical computations. The bifurcation graph which gives the bifurcation subgroups is determined from the interrelationship of the irreducible representations of a group and its subgroups. The Jacobian is transformed to block diagonal structure using a modification of the transformation which transforms to block diagonal structure with respect to a supergroup. The principle of conjugacy is used everywhere to make symbolic and numerical computations even more efficient. Finally, when the symmetry reduced problems and blocks of Jacobian matrices are evaluated numerically, the fact that the given representation is a quasi-permutation representation is exploited automatically.
    Keywords: ddc:000
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  • 13
    Publication Date: 2014-02-26
    Description: {\def\N{{\cal N}} \def\R{\hbox{\rm I\kern-2pt R}} \def\MN{{\rm I\kern-2pt N}} In this paper we study the following problem, which we call the weighted routing problem. Let be given a graph $G=(V,E)$ with non-negative edge weights $w_e\in\R_+$ and integer edge capacities $c_e\in\MN$ and let $\N=\{T_1,\ldots,T_N\}$, $N\ge 1$, be a list of node sets. The weighted routing problem consists in finding edge sets $S_1,\ldots,S_N$ such that, for each $k\in\{1,\ldots,N\}$, the subgraph $(V(S_k),S_k)$ contains an $[s,t]$-path for all $s,t\in T_k$, at most $c_e$ of these edge sets use edge $e$ for each $e\in E$, and such that the sum of the weights of the edge sets is minimal. Our motivation for studying this problem arises from the routing problem in VLSI-design, where given sets of points have to be connected by wires. We consider the weighted routing problem from a polyhedral point of view. We define an appropriate polyhedron and try to (partially) describe this polyhedron by means of inequalities. We briefly sketch our separation algorithms for some of the presented classes of inequalities. Based on these separation routines we have implemented a branch and cut algorithm. Our algorithm is applicable to an important subclass of routing problems arising in VLSI-design, namely to problems where the underlying graph is a grid graph and the list of node sets is located on the outer face of the grid. We report on our computational experience with this class of problem instances.}
    Keywords: ddc:000
    Language: English
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  • 14
    Publication Date: 2014-02-26
    Description: A new method for the numerical aproximation of an implicitly defined surface is presented. It is a generalization of the Euler- Gauss-Newton method for implicitly defined (one- parameter) curves to the case of (two-parameter) surfaces. The basic task in the more general case is an efficient combination of modern CAGD techniques (such as triangular Bernstein-Bzier patches and the nine parameter Hermite interpolant) and the rank deficient Gauss-Newton method.
    Keywords: ddc:000
    Language: English
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  • 15
    Publication Date: 2021-03-16
    Description: We propose an extended box method which turns out to be a variant of standard finite element methods in the case of pure diffusion and an extension of backward differencing to irregular grids if only convective transport is present. Together with the adaptive orientation proposed in a recent paper and a streamline ordering of the unknowns, this discretization leads to a highly efficient adaptive method for the approximation of internal layers in the case of large local Peclet numbers.
    Keywords: ddc:000
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  • 16
    Publication Date: 2014-02-26
    Description: Based on a simple stability analysis for the semi--implicit Euler discretization a new dynamic sparsing procedure is derived. This procedure automatically eliminates ``small'' elements of the Jacobian matrix. As a consequence, the amount of work needed to handle the linear algebra within a semi--implicit extrapolation integrator can be reduced drastically. Within the course of integration the sparsing criterion, which decides what ``small'' means, is dynamically adapted to ensure stability of the discretization scheme. Thus, stepsize restrictions due to instability can be avoided. Numerical experiments for quite different problems show robustness and efficiency of this dynamic sparsing technique. The techniques developed here in the context of stiff extrapolation integrators can, in principle, be applied to W--methods, where exact Jacobians may be replaced by ``sufficiently good'' approximations. {\bf Keywords:} Large scale integration, extrapolation methods, stiff ODEs, W--methods, sparse matrix techniques.
    Keywords: ddc:000
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  • 17
    Publication Date: 2014-02-26
    Description: In this paper we continue the investigations in [GMW92a] for the \def\sbppo{Steiner tree packing polyhedron} \sbppo. We present several new classes of valid inequalities and give sufficient (and necessary) conditions for these inequalities to be facet-defining. It is intended to incorporate these inequalities into an existing cutting plane algorithm that is applicable to practical problems arising in the design of electronic circuits.
    Keywords: ddc:000
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  • 18
    Publication Date: 2014-02-26
    Description: Subspace decompositions of finite element spaces based on $L2$-like orthogonal projections play an important role for the construction and analysis of multigrid like iterative methods. Recently several authors proved the equivalence of the associated discrete norms with the $H^1$-norm. The present report gives an elementary, self-contained derivation of this result which is based on the use of $ K$-functionals known from the theory of interpolation spaces. {\bf Keywords:} multilevel methods, nonuniform meshes, optimal convergence rates. {\bf AMS(MOS) Subject classifications:} 65N55, 65N30, 65N50.
    Keywords: ddc:000
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  • 19
    Publication Date: 2014-02-26
    Keywords: ddc:000
    Language: English
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  • 20
    Publication Date: 2014-02-26
    Description: Using the perturbational-variational Rayleigh-Ritz matrix formalism, the 1/Z-expansion for the ground state of the isoelectronic $H_2$ sequence in the range of the internuclear distance $0.2\le R \le 9.0$ is calculated. Also lower bounds of the radius of convergence, based on Kato's theory of linear operators, are given. The numerical results of the 1/Z-expansion can be compared with the exact results and do not converge in the whole R-range. This behavior is in qualitative agreement with the lower bounds for the radius of convergence and enlights some still open properties of 1/Z- expansions for this sequence in the literature. {\bf PACS:} 31.15 + q; 31.20 Di; 31.20 Tz.
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  • 21
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    Publication Date: 2019-10-24
    Keywords: ddc:000
    Language: German
    Type: annualzib , doc-type:report
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  • 22
    Publication Date: 2014-02-26
    Description: Let $\Re$ be the set of all binary relations on a finite set $N$ and $d$ be the symmetric difference distance defined on $\Re$. For a given profile $\Pi = (R_1,...,R_m) \in R^m$, a relation $R* \in \Re $ that minimizes the function $\sum^m_{k=1} d(R_k,R) $ is called a median relation of $\Pi$. A number of problems occuring in the social sciences, in qualitative data analysis and in multicriteria decision making can be modelled as problems of finding medians of a profile of binary relations. In these contexts the profile $\Pi$ represents collected data (preferences, similarities, games) and the objective is that of finding a median relation of $\Pi$ with some special feature (representing e. g., consensus of preferences, clustering of similar objects, ranking of teams, etc.). In this paper we analyse the computational complexity of all such problems in which the median is required to satisfy one or more of the properties: reflexitivity, symmetry, antisymmetry, transitivity and completeness. We prove that whenever transitivity is required (except when symmetry and completeness are also simultaneously required) then the corresponding median problem is $NP$-hard. In some cases we prove that they remain $NP$-hard when the profile $\Pi$ has a fixed number of binary relations.
    Keywords: ddc:000
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  • 23
    Publication Date: 2020-11-16
    Description: MEXX (short for MEXanical systems eXtrapolation integrator) is a Fortran code for time integration of constrained mechanical systems. MEXX is suited for direct integration of the equations of motion in descriptor form. It is based on extrapolation of a time stepping method that is explicit in the differential equations and linearly implicit in the nonlinear constraints. It only requires the solution of well--structured systems of linear equations which can be solved with a computational work growing linearly with the number of bodies, in the case of multibody systems with few closed kinematic loops. Position and velocity constraints are enforced throughout the integration interval, whereas acceleration constraints need not be formulated. MEXX has options for time--continuous solution representation (useful for graphics) and for the location of events such as impacts. The present article describes MEXX and its underlying concepts.
    Keywords: ddc:000
    Language: English
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  • 24
    Publication Date: 2019-05-10
    Description: We consider the approximate solution of selfadjoint elliptic problems in three space dimensions by piecewise linear finite elements with respect to a highly non-uniform tetrahedral mesh which is generated adaptively. The arising linear systems are solved iteratively by the conjugate gradient method provided with a multilevel preconditioner. Here, the accuracy of the iterative solution is coupled with the discretization error. as the performance of hierarchical bases preconditioners deteriorate in three space dimensions, the BPX preconditioner is used, taking special care of an efficient implementation. Reliable a-posteriori estimates for the discretization error are derived from a local comparison with the approximation resulting from piecewise quadratic elements. To illustrate the theoretical results, we consider a familiar model problem involving reentrant corners and a real-life problem arising from hyperthermia, a recent clinical method for cancer therapy.
    Keywords: ddc:000
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  • 25
    Publication Date: 2021-01-21
    Description: A Hamiltonian system subject to smooth constraints can typically be viewed as a Hamiltonian system on a manifold. Numerical computations, however, must be performed in $ R^n$. In this paper, canonical transformations from ``Hamiltonian differential--algebraic equations'' to ODEs in Euclidean space are considered. In \S2, canonical parameterizations or local charts are developed and it is shown how these can be computed in a practical framework. In \S3 we consider the construction of unconstrained Hamiltonian ODE systems in the space in which the constraint manifold is embedded which preserve the constraint manifold as an integral invariant and whose flow reduces to the flow of the constrained system along the manifold. It is shown that certain of these unconstrained Hamiltonian systems force Lyapunov stability of the constraint--invariants, while others lead to an unstable invariant. In \S4, we compare various projection techniques which might be incorporated to better insure preservation of the constraint--invariants in the context of numerical discretization. Numerical experiments illustrate the degree to which the constraint and symplectic invariants are maintained under discretization of various formulations. {\bf Keywords:} differential--algebraic equations, Hamiltonian systems, canonical discretization schemes. {\bf AMS(MOS):} subject classification 65L05.
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  • 26
    Publication Date: 2014-02-26
    Description: In this paper, two classes of second order accurate high resolution schemes are presented on regular triangular meshes for initial value problem of two dimensional conservation laws. The first class are called Runge-Kutta-FVM MmB (locally Maximum- minimum Bounds preserving) schemes, which are first discretized by (FVM) finite volume method in space direction and modifying numerical fluxes, and then by Runge-Kutta methods in time direction; The second class, constructed by Taylor expansion in time, and then by FVM methods and making modifications to fluxes, are called Taylor- FVM MmB schemes. MmB properties of both schemes are proved for 2-D scalar conservation law. Numerical results are given for Riemann problems of 2-D scalar conservation law and 2-D gas dynamics systems and some comparisons are made between the two classes of the schemes. Key words and phrases: MmB schemes, 2-D, conservation laws, gas dynamics systems, Runge-Kutta-FVM, Taylor-FVM.
    Keywords: ddc:000
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  • 27
    Publication Date: 2014-02-26
    Description: This paper deals with systems of $m$ polynomial equations in $n$ unknown, which have only finitely many solutions. A method is presented which decomposes the solution set into finitely many subsets, each of them given by a system of type \begin{displaymath} f_1(x_1)=0, f_2(x_1,x_2)=0,...,f_n(x_1,...,x_n)=0. \end{displaymath} The main tools for the decomposition are from ideal theory and use symbolical manipulations. For the ideal generated by the polynomials which describe the solution set, a lexicographical Gröbner basis is required. A particular element of this basis allows the decomposition of the solution set. A recursive application of these decomposition techniques gives finally the triangular subsystems. The algorithm gives even for non-finite solution sets often also usable decompositions. {\bf Keywords:} Algebraic variety decomposition, Gröbner bases, systems of nonlinear equations.
    Keywords: ddc:000
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  • 28
    Publication Date: 2014-02-26
    Description: A new adaptive approach for one-dimensional scalar conservation laws with convex flux is proposed. The initial data are approximated on an adaptive grid by a problem dependent, monotone interpolation procedure in such a way, that the multivalued problem of characteristic transport can be easily and explicitly solved. The unique entropy solution is chosen by means of a selection criterion due to LAX. For arbitrary times, the solutions is represented by an adaptive monotone spline interpolation. The spatial approximation is controlled by local $L^1$-error estimated. As a distinctive feature of the approach, there is no discretization in time. The method is monotone on fixed grids. Numerical examples are included, to demonstrate the predicted behavior. {\bf Key words.} method of characteristics, adaptive grids, monotone interpolation, $L^1$-error estimates {\bf AMS(MOS) subject classification.} 65M15, 65M25, 65M50.
    Keywords: ddc:000
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  • 29
    Publication Date: 2014-02-26
    Description: The matchings in a complete bipartite graph form a simplicial complex, which in many cases has strong structural properties. We use an equivalent description as chessboard complexes: the complexes of all non-taking rook positions on chessboards of various shapes. In this paper we construct `certificate $k$-shapes' $\Sigma(m,n,k)$ such that if the shape $A$ contains some $\Sigma(m,n,k)$, then the $(k{-}1)$-skeleton of the chessboard complex $\Delta(A)$ is vertex decomposable in the sense of Provan & Billera. This covers, in particular, the case of rectangular chessboards $A=[m]{\times}[n]$, for which $\Delta(A)$ is vertex decomposable if $n\ge 2m{-}1$, and the $(\lfloor{m+n+1\over3}\rfloor{-}1)$-skeleton is vertex decomposable in general. The notion of vertex decomposability is a very convenient tool to prove shellability of such combinatorially defined simplicial complexes. We establish a relation between vertex decomposability and the CL-shellability technique (for posets) of Björner & Wachs.
    Keywords: ddc:000
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  • 30
    Publication Date: 2014-02-26
    Description: The numerical solutions of Riemann problems in three, four, five and six pieces, which only contain contact discontinuities, are presented by using Taylor FVM MmB schemes on regular triangular meshes for 2-D gas dynamics systems. The 2-D Riemann initial data are as defined in [1], under the assumption that each jump in initial data outside of the origin projects exactly one planar wave of shocks, centered rarefaction waves , or contact discontinuities. The main ends of the paper are that spirals will be shown for some configurations and the relations of the solutions between different distibutions of Riemann initial data are explained by the numerical solutions of modified Riemann problems. Key words and phrases: Riemann problem, gas dynamics systems, spiral, MmB schemes.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 31
    Publication Date: 2014-02-26
    Description: Whereas optimization of a linear function over an efficient set is a favourite topic for theoretical studies, the problem ($P^I$) of finding a maximal value of a linear function $dx$ over an integer efficient set is still open. The problem ($P^I$) is NP-hard and it is very unlikely that the maximal objective value of the integer problem ($P^I$) in many cases is greater than the maximal objective value of it's corresponding continuous problem ($P$). In this paper we pay atention to the study of the problem ($P^I$) and some related properties of the problem ($P$). In particular, we establish conditions determining whether or not an optimal solution to the problem ($P$) is an optimal solution to the it's corresponding linear program. For the problem ($P^I$) we find an upper bound for it's optimal objective value and present an algorithm which gives a global optimal solution after a finite number of steps. We also study two particular classes of problems ($P^I$) : the bicriteria case and the case when $d$ is a nonnegative linear combination of the vectors-criteria defining the efficient set. Key words: Multiple objective linear programming, integer efficient set, efficient cone, cutting plane.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 32
    Publication Date: 2014-02-26
    Description: Two commercially available molecular electronic structure software packages GAUSSIAN90 and GAMESS-UK are compared. Basis for this comparison is a benchmark suite which is designed to highlight the typical range of calculations commonly performed by the ab initio computational chemist.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 33
    Publication Date: 2014-02-26
    Description: The following report intends to provide a survey over the computational chemistry molecular structure software installed on the supercomputers CRAY X-MP/216 and CRAY Y-MP2E/164 at ZIB. It shows what kind of problems can be tackled with the existing chemistry software, which covers a wide range of ab initio, semiempirical, molecular mechanics, and dynamics applications.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 34
    Publication Date: 2014-02-27
    Description: Die vorliegende Arbeit beschäftigt sich mit dem Plazierungsproblem, welches beim Entwurf elektronischer Schaltungen auftritt. Das Plazierungsproblem modellieren wir als ein quadratisches 0/1 Optimierungsproblem unter linearen Nebenbedingungen und untersuchen das Modell komplexitätstheoretisch. Der zweite Aspekt der Arbeit bezieht sich auf die Lösung praktischer Problembeispiele im sogenannten Sea of cells"-Entwurfsstil. Zur Lösung dieser Beispiele wurde ein Prototyp implementiert und mit state of the art"-Plazierungsverfahren verglichen. Schlie\ss lich werden wir uns mit dem Clusteringproblem, das eine Variante des Mehrfachschnitt-Problems darstellt, beschäftigen. Dabei steht einerseits im Vordergrund, wie diese Probleme heuristisch gelöst werden können und wie die Integration des Ansatzes in das Plazierungsprogramm erfolgt. Andererseits soll das Clusteringproblem polyedrisch untersucht werden.
    Keywords: ddc:000
    Language: German
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
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  • 35
    Publication Date: 2014-02-26
    Description: This report presents new codes for the numerical solution of highly nonlinear systems. They realize the most recent variants of affine invariant Newton Techniques due to Deuflhard. The standard method is implemented in the code NLEQ1, whereas the code NLEQ2 contains a rank reduction device additionally. The code NLEQ1S is the sparse version of NLEQ1, i.e. the arising linear systems are solved with sparse matrix techniques. Within the new implementations a common design of the software in view of user interface and internal modularization is realized. Numerical experiments for some rather challenging examples illustrate robustness and efficiency of algorithm and software.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/postscript
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  • 36
    Publication Date: 2014-02-26
    Description: In this paper we describe a modular implementation of the well-established extrapolation codes EULEX, EULSIM and DIFEX for initial value problems of ordinary differential equations. The basic module embodies an abstract extrapolation method with order and stepsize control. Based on this module the particular integration codes only have to provide the underlying discretization schemes.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 37
    facet.materialart.
    Unknown
    Publication Date: 2014-02-26
    Description: Scientists intending to employ scientific visualization techniques are confronted with the unpleasant task of choosing visualization software that meets their specific needs. A good choice requires consideration of several aspects. Most important are functionality, i.e. the set of supported visual representations, and restrictions due to the user's production environment (i.e. available hardware and software platforms, software compatibility constraints, need of specific input and output formats, network distribution requirements). Crucial are quality demands, ranging from simple graphics for interactive control of simulations, to images of highest quality (glossy prints, slides or video movies) for presentation purposes. Further aspects of consideration are: ease of use, level on which the user is willing to program, portability, conformity to prevalent standards, availability in the world-wide user community, future dissemination, as well as emerging trends in computer graphics and scientific visualization. The aim of this manual is to give a survey on the graphics and visualization software that is currently being provided at ZIB (mainly for internal use). The whole range of computer graphics software relevant in mathematical, natural and technical sciences is covered: image synthesis (basic and higher graphics libraries, plot programs, visualization environments, combined text and drawing programs, renderers), image processing and storage (raster and vector formats, page description languages, raster toolkits for image processing and format conversion), capturing of images as well as printing on paper and recording on photographic film or video tape. This information together with a glossary and recommendations for further reading should help prospective users in getting started and assist them in making good choices of graphics and visualization software.
    Keywords: ddc:000
    Language: German
    Type: reportzib , doc-type:preprint
    Format: application/postscript
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  • 38
    Publication Date: 2014-02-26
    Description: Im Bereich der Mathematik entwickelte sich in Deutschland die elektronische Fachinformation in Form der Online-Datenbank MATH und der CD-ROM CompactMATH auf der Grundlage der Arbeiten des Referateorgans "Zentralblatt für Mathematik und Ihre Grenzgebiete". Das "Zentralblatt" fand weithin Anerkennung und Verbreitung. Die Rezeption elektronischer Fachinformation ging jedoch - nicht nur im Bereich der Mathematik - nur zögerlich vonstatten. Die Gründe dafür werden in einer vom Bundesminister für Forschung und Technologie (BMFT) initiierten Studie analysiert. Ein kürzlich von der Deutschen Mathematiker - Vereinigung begonnenes und vom BMFT gefördertes Vorhaben hat die "Verbesserung des benutzerorientierten Zugriffs auf fachspezifische Online-Datenbanken und CD-ROM für Mathematische Institute in der Bundesrepublik Deutschland" zum Ziel. Insgesamt 51 mathematische Fachbereiche und Institute nehmen daran teil. Elektronische Fachinformation soll zu einem festen Bestandteil des methodischen Instrumentariums der wissenschaftlichen Arbeit werden. Diese Schrift soll die Ausgangslage in den Fachbereichen darstellen und die organisatorischen und technischen Infrastrukturmaßnahmen erläutern, mit denen den spezifischen Nutzungshemmnissen begegnet werden soll.
    Keywords: ddc:000
    Language: German
    Type: reportzib , doc-type:preprint
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  • 39
    ISSN: 1573-5028
    Keywords: Brazil nut ; 2S albumin gene ; gene transfer ; Phaseolus vulgaris ; particle bombardment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Bean (Phaseolus vulgaris L.) mature embryos were transformed using biolistic methods with a plasmid containing 2S albumin and β-glucuronidase structural sequences, both under the control of the 35S CaMV promoter. We have shown that chimaeric tissues could be obtained and that both structural sequences were expressed to similar levels.
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  • 40
    ISSN: 1573-5044
    Keywords: Agrobacterium transformation ; Cucumis sativus ; gene transfer ; neomycin phosphotransferase ; tissue culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Cucumber (Cucumis sativus L.) petiole and leaf segments of two pickling genotypes were transformed with Agrobacterium tumefaciens strain LBA 4404, an octopine Ti-plasmid deletion mutant that is avirulent (disarmed plasmid), but to which were added T-DNA inserts on binary plasmids (pBIN 19, ca. 10 kb, and pCGN 783, ca. 25 kb). Expression of neomycin phosphotransferase (NPT II) encoding resistance to the aminoglycoside kanamycin was used as a selectable marker. Factors which influenced the frequency of callus development on medium containing kanamycin (75 mg l-1) were explant size, bacterial concentration and length of exposure, cocultivation period, and presence of acetosyringone. The optimal procedure involved exposing segments of petiole (4–6 mm) or leaf (0.5 cm2) segments to a bacterial suspension (108 cells ml-1) containing 20 μM acetosyringone for 5 min, followed by a 48 h cocultivation period on a tobacco feeder layer. Explants were placed on MS medium containing 500 mg l-1 carbenicillin, 75 mg l-1 kanamycin, and NAA/BA (5.0/2.5 μM) or 2,4-d/BA (5.0/5.0 μM) and subcultured twice, each after a 2–3 week period, onto fresh media. The overall frequency of transformed callus was 20–50%; the frequency of plantlet regeneration from transformed callus was 8–15%. Twenty-one out of 23 individual plants recovered from two genotypes of pickling cucumber were NPT II positive (transformation frequency of 9%). Copy number of the NPT II gene insert (35S-NPT II-3′ fragment, ca. 2.2 kb) in three transformed plants was estimated at ten per haploid genome, indicative of multiple insertions within the cucumber genome. Multimers of the gene (visible as 4.4 and 6.6 kb fragments in Southern analysis) were detected in one plant, suggestive of tandem duplications or repeats. Progeny from a cross between this transformed plant and a nontransformed control showed segregation for the NPT II gene in dot-blot assays; at least 24 plants out of 32 were kanamycin positive. Copy number in the progeny was variable, and ranged from none to ten.
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  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 139-150 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe makroporöser Glycidylmethacrylat-Ethylendimethacrylat-Copolymerer (GMA-co-EDMA) wurde durch Suspensionspolymerisation hergestellt; dabei wurden nach einer statistisch geplanten experimentellen Durchführung die Ethylendimethacrylatkonzentration und die Heizrate der Polymerisationstemperatur von 20 auf 70°C variiert. Die Porositätseigenschaften der hydrolysierten Copolymeren wurden mit Hilfe der Größenausschlußchromatographie unter Verwendung von Polystyrolstandards in Tetrahydrofuran charakterisiert. Das Porenvolumen, die spezifische Oberfläche und die Porengröße werden dabei durch die Konzentration des Vernetzungsmittels stärker beEinflußt als durch die Heizrate während der Polymerisation.
    Notes: A series of macroporous glycidyl methacrylate-ethylene dimethacrylate copolymers have been prepared by the suspension polymerization according to a statistical design of experimental approach in which concentration of ethylene dimethacrylate and time needed for raising the polymerization temperature from 20 to 70°C have been varied. The porous properties of hydrolyzed copolymers have been characterized by means of size exclusion chromatography using polystyrene standards in tetrahydrofuran. Pore volume, specific surface area, and pore size are affected by the crosslinking agent concentration rather than by the rate of temperature increase during the polymerization reaction.
    Additional Material: 2 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 171-190 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Copolymers of AN were prepared with variable molecular masses and with variable contents of methylacrylate (ASME) and sodiumallylsulfonate (NaAS), acrylamide (AA), itaconic acid (IS), polyethyleneglycol acrylate (600) (PEGA), vinylacetate (VA), 2-hydroxyethyl acrylate, (HEE) or sodium acrylamido-2-methylpropanesulfonate (NaAMPS), respectively, by using a mathematical model for the calculation of the polymerization conditions needed. Precipitation studies by light scattering showed the predominant influence of NaAS and NaAMPS on the precipitation properties. Acrylonitrile homopolymers show a hard precipitation behaviour. The originating particles have a density of between 0.2 and 0.4 g/cm3. An increasing content of NaAS or NaAMPS leads for example beginning from 0.8 wt.-% NaAS in the monomer composition to a soft precipitation behaviour and to highly swollen particles possessing a density of less than 1 · 10-2 g/cm3. The molar mass and the ASME-content show no significant influence. For the acrylonitrile/acrylamide system already 0.5 wt.-% allylsulfonate is sufficient to get a soft precipitation behaviour with formation of highly swollen particles. All samples with the other cocomponents and without NaAS- or NaAMPS-comonomer show a hard precipitation behaviour with little swollen particles.
    Notes: Copolymere des Acrylnitrils (AN) mit variabler Molmasse bzw. mit variablem Anteil von Acrylsäuremethylester (ASME) und Natriumallylsulfonat (NaAS), Acrylamid (AA), Itaconsäure (IS), Polyethylenglykolacrylat (600) (PEGA), Vinylacetat (VA), Acrylsäure-2-hydroxyethylester (HEE) oder Natrium-2-acrylamido-2-methylpropansulfonat (NaAMPS) wurden hergestellt, wobei die erforderlichen Polymerisations-bedingungen mit Hilfe eines mathematischen Polymerisationsmodells ermittelt wurden.Die Fällungsuntersuchungen mit der Methode der Lichtstreuung zeigten, daß NaAS und NaAMPS einen dominierenden Einfluß haben. Bei Acrylnitril-Homopolymeren tritt eine harte Fällung auf, und die entstehenden Partikel haben eine Dichte zwischen 0,2 und 0,4 g/cm3. Zunehmender NaAS-bzw. NaAMPS-Gehalt führt ab einem Gehalt von beispielsweise ca. 0,8 Gew.-% NaAS im Monomergemisch zu einer weichen Fällung, bei der hochgequollene Partikel mit einer Dichte in der Größenordnung von 〈 1.10-2 g/cm3 entstehen. Ein Einfluß der Molmassen und des ASME-Gehaltes Konnte nicht nachgewiesen werden. Beim Acrylnitril/Acrylamid-System genügen offensichtlich 0,5 Gew.-% Allylsulfonat im Monomeransatz, um eine stabile, weiche Fällung unter Bildung hochgequollener Strukturen zu gewährleisten. Alle Proben mit den übrigen hydrophilen Cokomponenten zeigen ohne NaAS bzw. NaAMPS-Comonomer ein hartes Fäungsverhalten mit wenig gequollenen Partikeln.
    Additional Material: 4 Ill.
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  • 43
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 191-204 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Photovernetzung von Poly(p-hydroxystyrol) (PPHS) wird durch O2 beachtlich beschleunigt. Dies ergab sich aus der Bestimmung der Molmasse (mit Hilfe der Lichtstreumethode) und des Gelanteils nach kontinuierlicher Bestrahlung bei λinc = 254 nm. Aufgrund von Ergebnissen aus Blitzphotolyseversuchen wird der folgende Reaktionsmechanismus aufgestellt: Die Vernetzung sowohl in An-als auch Abwesenheit von O2 kommt im wesentlichen durch Kombination von Radikalen des Phenoxyltyps zustande. In Abwesenheit von O2 werden Phenoxylradikale ausschließlich durch Spaltung von O—H-Bindungen phenolischer Gruppen, die sich im angeregten Singulettzustand befinden, erzeugt. Triplett-angeregte phenolische Gruppen, die sich auch bilden, desaktivieren nicht durch Spaltung der O—H-Bindungen. Sie reagieren allerdings sehr effektiv, sofern vorhanden, mit O2. Bei dieser Reaktion entstehen HO·2- und zusätzliche Phenoxylradikale. Alle handelsüblichen und die meisten im Labor synthetisierten PPHS-Proben enthalten chemisch gebundene, chinoidartige Verunreinigungen. Durch Versuche mit niedermolekularen Modellverbindungen wurde nachgewiesen, daß triplett-angeregte chinoide Gruppen einerseits mit phenolischen Gruppen unter Bildung von Phenoxylradikalen reagieren und daß sie andererseits unreaktiv sind bezüglich der Abstraktion aliphatischer Wasserstoffatome. Die Bestrahlung von PPHS bei λinc = 254 nm bewirkt die Bildung chinoider Gruppen, die bei dieser Wellenlänge auch stark absorbieren. Die Lichtabsorption dieser Gruppen wird im Laufe der weiteren Bestrahlung zum bestimmenden Faktor hinsichtlich der photochemischen Veränderung des Polymeren.
    Notes: Light-induced crosslinking of poly(p-hydroxystyrene) (PPHS) is significantly enhanced by O2. This was evidenced by molar mass (light scattering measurements) and by gel content determinations which were performed on various polymer samples before and after continuous irradiation at λinc = 254 nm. The following mechanism was elucidated with the aid of flash photolysis studies: Crosslinking in the absence or presence of O2 is mainly due to the combination of phenoxyl type radicals. In the absence of O2 the latter are exclusively formed by O—H bond cleavage of singlet excited phenolic groups. Triplet excited phenolic groups which are also formed do not deactivate via O—H bond cleavage but react very effectively with O2. This reaction leads to the formation of HO2· and additional phenoxyl type radicals. All Commercial and most laboratory-prepared PPHS samples contain chemically bound impurities of quinoid nature. On the basis of results performed with model compounds of low molar mass, it is concluded that triplet excited quinoid groups react effectively with phenolic groups forming phenoxyl type radicals and that they are quite unreactive with respect to the abstraction of alphatic hydrogen atoms. Irradiation of PPHS at λinc = 254 nm causes the formation of quinoid groups which absorb strongly at this wavelength. Light absorption by these groups becomes a determining factor with respect to photochemical alteration in the course of further irradiation.
    Additional Material: 9 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 21-35 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die verschiedenartigen Eigenschaften von Polymerlegierungen aus Polyoxymethylen (POM) und bis zu 20 Gew.-% chemische oberf;ächenbehandeltem Poly(tetrafluorethylen) (CPTFE) wurden untersucht und denen unbahandelter POM/PTFE- Blends gegenübergestellt. PTFE iwrd POM zugesetzt, um dessen Oberflächenabriebseigenschaften Anteil zunehmend verschlechtert. Durch die bessere Phasenanbindung in den oberflächenbehandelten POM/CPTFE- Blends konnten die doppelten Zugfestigkeiten und EModuli wie bei unbehandelten POM/PTEF- Blends erreicht werden. Mit Hilfe der Elektronenmikroskopie (SEM) konnte gezeigt werden, daß die PTEF-Agglomerate in der POM-Matrix eine Größe von 30 bis 100 μm haben, während die CPTFE-Teilchengrößbe unter 1 μum liegt.
    Notes: The various properties of the blends of polyacetal (POM) with up to 20 wt.-% chemically surface-treated poly(tetrafluoroethylene) (CPTFE) were investigated and compared with those of POM/PTFE blends. The PTFE is added to POM to improve the wear properties, however, the mechanical properties of POM/PTFE blends decrease with increasing PTFE content, but tensile strength and Young's modulus of POM/CPTFE blends are more than 2 times higher than that of the POM/PTFE blends. SEM shows that the size of inherent agglomerative PTFE is in the range of 30 to 100 μm. The particle size of major CPTFE dispersed in POM is smaller than 1 μm.
    Additional Material: 12 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 49-61 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Hydrogele wurden aus methylmethacrylat (MMA) and N-Vinyl-2-pyrrolidon (NVP) mit 1,2,2-Trimethylolpropantrimethacrylat (TPTA) als Vernetzungsmittel hergestellt. Die Terplymerisation wurden mittels UV-strahlung (365 nm) initiiert, wobei kleine Mengen an Diethoxycetophenon (DEAP) als Photosensibilisator sowie Triethanolamin(TEA)als Beschleuniger und Verdünner verwendet wurden. Die Hydrogele wurden durch Messung des Wasserrückhaltevermögens, der Sauerstodiffusions- und permitionskoeffizienten, der mechanischen Eigenschaften und der Lichtdurchlässigkeit charakterisiert. Dabei zeigte sich, daß die Hydrogele bis zu 80 Gew.-% Wasser aufnehmen können, wobei mit steigendem Wassergtehalt deren mechanische Festigkeit drastisch sinkt. Der Ssuerstoffdiffusionskoeffizient der gequollenen Hydrogele beträgt 10-6 cm2s-1, der Sauerstoffpermeationskoeffizient 1013 cm2s-1Pa-1, und die Lichtdurchlässigkeit liegt im Bereich von 500 bis 700 nm bei über 90%.
    Notes: Hydrogels are synthesized from methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (NVP) with 1,1,1-trimethylol propane trimethacrylate (TPTA) as a crosslinking agent. It was polymerized under UV radiation (365nm) with a small amount of photosensitizer, diethoxy acetophenone (DEAP), acclerator and diluent, triethanol amine (TEA). The hydrogels were characterized by measuring the water retention, dissolved oxygen diffusivity and permeability, mechanical strength, and light transparency. The hydrogels can retain water up to 80 wt.-% and the mechanical strenght is weakened as the water content is increased in the gel. The dissolved oxygen diffusivity and permeability in the swelling hydrogels are determined to be 10-6 cm2/sec and 1013 cm2s-1 Pa-1, respectively. The light transparency is over 90% in the wave lenght ranging from 500 to 700 nm.
    Additional Material: 5 Ill.
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  • 47
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Bisphenol-A-Epoxidharz wurde zunächst mit Toluylendiisocyanat, dessen eine Isocyanatgruppe mit 2-Ethylhexanol blockiert war, und dann mit unterschiedlichen Mischungen on Diethanolamin und Bis(2-methyl-isobutylketiminoethyl)amin (DKI)umgesetzt. Aus diesen Harzen mit Triethanolamin- und DKI-Endgruppen wurden durch Hydrolyse und Neutralisieren mit Essigsäure kationische Harze mit primären Amin-Endgruppen erhalten, aus denen mit geeigneten Lösungsmitteln und deionisiertem Wasser Emulsionen hergestellt wurden. Deren Eigenschaften und die Elektroabscheidung der Harze aus den Emulsionen wurden untrsucht. Der Effekt der Zugabe von hydrophoben Lösungsmitteln wie Toluol oder Hexylcellosolv (HCS) auf die Abscheidungseigenschaften wird diskutiert.
    Notes: A diglycidylether of bisphenol A epoxy resin (DGEBA) was first reacted with 2,4-toluene diisocyanate partially blocked with 2-ethylhexanol (2-EH P. B. TDI) to form modified epoxy resins, and subsequently reacted with different molar ratios of diethanolamine and bis(2-methylisobutylketiminoethyl)amine (DKI) (used as ring opening agents) to give diethanolamine/diketimine terminated resins. These resins were hydrolyzed and neutralized with acetic acid to give cationic resins containing various contents of primary amine groups in the terminal polymeric chain. These cationic resins can be dissolved in a suitable solvent and mixed with deionized water to obtain emulsions. The electrodeposition properties and characteristics of the resulting cationic resins were investigated in detail. The effects of hydrophobic solvents, such as hexyl cellosolve (HCS) and toluene, on the deposition properties of the emulsions are discussed.
    Additional Material: 11 Ill.
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 107-111 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalische Polymerisation von Acrylnitril in Gegonwart verschiedener ungesättigter optischer Aufheller (FB) (Derivate des 1,3,5-Triazins) wurde untersucht. Kolorimetrische Messungen ergaben, daß mehr als 80% des optischen Aufhellers in die Polymerkette eingebaut werden. Zur Erzielung eines intensiven optischen Effektes genügt eine FB-Anfangskonzentration von 0,1 Gew.-%, bezogen auf Acrylnitril.
    Notes: The polymerization of acrylonitrile in the presence of some unsaturated, triazinebased fluorescent brighteners (FB) has been investigated. It was found colourimetrically that more than 80% of the FB is incorporated in the polymer. The initial concentration of 0.1 wt.-% is sufficient to obtain a good bleaching effect without significant decrease of the molecular weight.
    Additional Material: 2 Ill.
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  • 49
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Les polyesters thermoplastiques (PBT et PET) sont des polymères fragiles avec une résistance au choc entaillée faible. Leur renforcement peut être obtenu par extrusion réactive avec dirrérents types de copolymères élastomères de l'éthylène, contenant des fonctons à réactivité potentielle avec extrémités de chaîne acide et hydroxyle des polyesters.Deux types de copolymères ont été étudiés: Ethylène(acrylate d'éthyle/méthacrylate de glycidyle (E/EA/GMA), et éthylène/acrylate d'éthyle/anhydride maléique (E/EA/MAH). Les alliages ont été obtenu par malaxage de 10 à 25% de coppolymères avec du PBT.Le PBT présente une transition fragile, ductile lorsqu'on passe de 10 à 20% de particules dispersées de copolymère au GMA. Les gains les plus importants en résistance au choc sont obtenus en réticulant partiellement la phase dispersée, par association de copolymères en GMA et de copolymères avec MAH et catalyseur de réaction.
    Notes: Poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) are brittle polymers with poor notched impact strength. Their toughening can be achieved by melt blending with different types of rubbery ethylene copolymers containing functions having potential reactivity with the hydroxy and carboxy end groups in polyesters.Two types of ethylene copolymers were investigated: ethylene/ethyle acrylate/glycidyl methacrylate (E/EA/GMA) and ethylene/ethyl acrylate/maleic anhydride (E/EA/MAH) copolymers. The blends were obtained by reactive extrusion of PBT with 10 to 25% of copolymers.PBT blends undergo a brittle to ductile transition by toughening with GMA copolymer between 10 and 20% of rubbery phase. The most effective toughening could be achieved by a partial crosslinking of the rubbery particles obtained by associating GMA and MAH copolymers and a reaction catalyst.
    Additional Material: 5 Ill.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 101-106 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Orientierung (Neigungswinkel ϕ) von thermotropen Flüssigkristallen (LC) an der Grenzfläche zu polymerbeschichteten Substraten wird nicht nur durch den numerischen Wert der Oberflächenspannung \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} bestimmt. Das Verhältnis zwischenden dispersiven und polaren Anteilen an \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} beeinflußt ebenfalls die Orientierung der LC-Moleküle an der Substratoberfläche. Als Polymere wurden ein Polyimid und ein Midgruppenhaltiges Styrol/Maleinsäureanhydrid-Copolymeres verwendet.
    Notes: The orientation (tilt angle ϕ) of thermotropic liquid crystals (LC) on the interface to a polymer-coated surface is not only determined by the numerical value \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} of the substrate surface tension. However, the ratio between the dispersive and the polar part of \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm\gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} also influences the LC orientation on the substrate surface. A polyimide and an amide-modified styrene/maleic anhydride copolymer were used as polymers.
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 129-137 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Epoxidharze aus Bisphenol A wurden mit neuen Diphenolen, die Imidgruppen enthalten, modifiziert, um die thermischen Eigenschaften zu verbessern. Die verwendeten Diimiddiphenole wurden aus Dianhydriden und Aminophenolen durch Kondensation hergestellt. Die Diimiddiphenole und die modifizierten Harze wurden durch IR- und NMR-spektroskopische Messungen charakterisiert. Das thermische Verhalten wurde anhand von DSC- und TGA-Messungen untersucht.
    Notes: Epoxy resins derived from Bisphenol A have been modified with new diphenols containing imide moieties in order to improve their thermal properties. The diphenols have been synthesized from dianhydrides and aminophenols by condensation reactions. Diphenols as well as modified resins have been characterized by IR and NMR spectroscopy. The thermal characteristics were evaluated by DSC and TGA.
    Additional Material: 3 Ill.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 165-170 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The structural transformation of a molecular complex (MC) of polyoxyethylene and urea on cooling from the molten state has been investigated by DSC and X-ray analysis. A high-temperature polymorphic from of the MC was found to be formed, which transforms into the known crystal form of the MC with a hexagonal crystal modification on cooling.
    Notes: Die Strukturveränderungen eines Molekülkomplexes (MK) aus Polyoxyethylen und Harnstoff beim Abkühlen aus dem geschmolzenen Zustand werden kalorimetrisch und röntgenographisch untersucht. Es wird festgestellt, daß eine polymorphe Hochtemperaturform des MK entsteht, die beim Abkühlen in die bekannte Kristallform des MK mit hexagonaler Kristallmodifikation übergeht.
    Additional Material: 3 Ill.
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  • 53
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 143-154 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Anfangsstadium der Oxidation von Lactamen wurden im Temperaturbereich 70-120°C Cuntersucht. Es wurde festgestellt, daß Pyrrolidon und Piperidon bedeutend schneller oxidiert werden als die sieben-, acht- und dreizehngliedrigen Lactame sowie lineare N-Alkylamide. Die hohe Oxidierbarkeit der fünf- und sechsgliedrigen Lactame kann der leichteren homolytischen Spaltung der N- vicinalen C—H Bindung und der unterschiedlichen Reaktivität der Lactamradikale im Wachstuschritt der Kettenoxidation zugeschrieben werden.
    Notes: The initial stage of oxidation of lactams was studied in the temperature range 70-120°C. It was found that pyrrolidone and piperidone are oxidized essentially more easily than the seven-, eight-, nine- and thirteen-membered lactams as well as linear N-alkylamides. The high oxidizability of the five- and six-membered lactams may be attributed to the easier homolytic splitting of the N-vicinal C—H bond and to the different reactivity of lactam radicals in the propagation step of the chain oxidation.
    Additional Material: 5 Ill.
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  • 54
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 127-141 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The relative chain transfer constant for sodium allylsulfonate (NaAS) in the copolymer system acrylonitrile (AN)/methylacrylate (MA) in dimethylformamide (DMF) was determined to be Cx = 0,04 ± 0.01, independent of the initiator used (azoisobutyronitrile, ammoniumperoxodisulfate).The chain transfer reaction explains the influence of NaAS on the polymerization degree, but not the concentration dependence of the copolymerization reactivity ratio r1 · r1 depends on the transfer reaction only in a range of 1 - 5%.The extended Debye-Hückel theory for dilute electrolytes has been successfully tested for a quantitative dependence of r1 from NaAS concentration. The resultant r10-value for infinite dilution of NaAS obviously depends on the acrylonitrile concentration, but only to a small extent (e.g. r10 = 0.32 for [AN] =- 4.26 mol/l). This theory provides comfortable access to resolve the nonideal AN/NaAS copolymerization. This approach may be generally applicable to copolymerizations of monomers with dissociated groups.
    Notes: Im Copolymerisationssystem Acrylnitril (AN)/Methylacrylat(MA) mit Natriumallylsulfonat (NaAS) in Dimethylformamid wurde die relative Übertragunskonstante zum NaAS Cx = 0,04 ± 0,01 unabhängig vom verwendeten Initiator (Azoisobuttyronitril, Ammoniumperoxodisulfat) ermittelt. Die Übertragunsreaktion beschreibt den Einfluß des NaAS auf den Polymerisationsgrad, sie beeinflußt jedoch den Copolymerisationsparameter r1 nur in der Größenordung von 1 bis 5% und kann damit die Konzentrationsabhängigkeit von r1 nicht erklären.Mit Hilfe der erweiterten Debye-Hückel-Theorie für verdünnte Elektrolyte wird die Abhängigkiet des r1-Wertes von der NaAS- Konzentration beschrieben. Der sich daraus für unendliche Verünnung des NaAS ergebende r10-Wert ist offensichtlich noch gerinfügig von der Acrylnitrilkonzentration abhägig. Er liegt beispielsweise für [AN] = 4, 26 mol/1 bei r10 = 0, 32. Damit wurde zum ersten Mal das nichtideale Copolymerisationsverhalten im untersuchten System erkärl. Das Vorgehen sollte verallemeinerungsfähig sein und generell auf das Copolymerisationsverhalten von Monomeren mitdissoziierten Gruppen angewendet werden können.
    Additional Material: 4 Ill.
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  • 55
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 169-177 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Katalase wurde durch photoinduzeirte Propfpolymerisation auf mikroporöse polymere Trägermembranen immobilisiert. Die katalytische Aktivität für Zersetzung von Wasserstoffperoxid unter Ultrafitrationsbedingungen wurde mittels eines Rezirkulationsapparates untersucht. Die Membranen zeigten ein sehr gutes katalytisches Verhalten; die Enzymreaktion fand ausschließlich in der Membranstruktur statt. Anfangsreaktionsgeschwindigkeiten, gemessen in einem Temperaturbereich von 5-35°C als Funkation der Substratkonzentration und der Menge des immobilisierten Enzyms pro Einheit Membranoberfäche zeigten, daß sich der Reaktionsmechanismus der Katalase durch die Immobilisierung nicht verädert.
    Notes: Catalase has been immobilized in membranes prepared by photoinduced grafting onto microporous polymeric supports and its catalytic activity on hydrogen peroxide decomposition has been studied under ultrafiltration conditions by means of a recirculation apparatus. The membranes showed a very good catalytic performance and the enzyme reaction took place exclusively within the membrane structure. Initial reaction rates measured in the temperature range 5 - 35°C as a function of both substrate concentration and enzyme amount immobilized per unit membrane surface indicate that the mechanism of action of catalase is not altered after immobilization.
    Additional Material: 2 Ill.
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  • 56
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The network formation process of bisphenol A-diglycidylether and 4,4′-diaminodiphenylmethane was investigated by measuring the torque, the conductivity and the soluble part of the crosslinking system. The activation energy for the curing process was estimated from gel time. The volume shrinkage during network formation was measured. The influence of N,N-dimethylbenzylamine as accelerator was discussed.
    Notes: Der Aufbau von Netwerken aus Bisphenol A-Diglycidylether und 4,4′-Diaminodiphenylmethan wurde durch Messung des Drehmomentes, der Leitfähigkeit und durch Bestimmung der löslichen Anteile des vernetzenden System untersucht. Aus den Gelzeiten wurden die Aktivierungsenergie für den Vernetzungsprozeß bestimmt. Außerdem wurde die während der Vernetzung aufretende Volumenschwindung gemessen. Der Einfluß von N, N-Dimethylbenzylamin als Beschleuniger auf den Vernetzungsprozeß wird diskutiert.
    Additional Material: 6 Ill.
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  • 57
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The UV-laser induced surface modification of various types of high-performance fibers is investigated. Due to the high UV-absorption coefficients, the well-known effect of UV-laser induced etching (ablation) is observed with all fiber types. Furthermore, the relaxation of orientated macromolecules leads to a characteristic structuring of the fiber surface. For a possible controlled use of this physical surface modification, exact conditions for the treatment in view of textile applications are determined. Useful constants like threshold of ablation, etching rate and structuring constants are measured for all fiber types.
    Notes: Die Oberflächenbehandlung von unterschiedlichen Hochleistungsfasertypen mit gepulstem UV- Laserlicht wird untersucht. Bedingt durch die hohen UV-Absorptionskoeffizienten dieser Materialien wird der bekannte Effekt des UV-laserinduzierten Abtrags (Ablation) bei allen Fasern beobachtet. Zusätzlich werden durch die Relaxation der orientierten Makromoleküle charakteristische Strukturierungen auf der Faseroberfläche ausgebildet. Für einen möglichen kontrollierten und gezielten Einsatz dieser physikalischen Oberflächenmodifizierung in textilen Anwendungen werden die gnaunen Bedingungen der Laserbestrahlung ermittelt und beschieben. Darüber hinaus werden geeignete Konstanten der Laserbearbeitung wie Ablationsschwellenenergie, Ätzraten und Strukturierungskonstanten für verschiedene Fasertypen bestimmt.
    Additional Material: 8 Ill.
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  • 58
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 165-178 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation von Dimethyl-diallyl-ammoniumchlorid in konzentrierter wäßriger Lösung mit Persulfat als Initiator kann bis zu hohen Umsätzen mit einem Modell beschrieben werden, in dem folgende Teilreaktionen berücksichtigt werden: a)Primärradikalbildung durch aktivierten Initiatorzerfall sowie Redoxreaktion von S2O2-8 und Cl-b)Kettenwachstum über Monomerkationassoziate undc)Kettenabbruch durch Kombination von cyclisierten Polymerradikalen untereinan der und mit Chloratomen.Für die Polymerisationsgeschwindigkeit wird ein Zeitgesetz hergeleitet, für dessen Konstanten und Parameter numerische Werte ermittelt wurden.
    Notes: The polymerization of dimethyl diallyl ammonium chloride in concentrated aqueous solution with persulfate as an initiator can be described up to high conversion by a kinetic model including a)formation of primary radicals by activated initiator decomposition as well as by redox reaction of S2O82- and Cl-,b)chain propagation via monomer cation associates andc)termination by combination of cyclized polymer radicals between each other or with chlorine atoms.A kinetic expression for the rate of polymerization is presented; rate constants and model parameters have been determined.
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  • 59
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 199-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 60
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 179-190 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymere mit über eine C—C-Verknüpfung an hochvernetztem Polystyrol kovalent gebundenen, makrocyclischen Amiden wurden durch die Reaktion polymergebundener Malonsäureester-Gruppen mit offenkettigen Diaminen dargestellt. Die Reaktion von vernetztem, chlormethyliertem Polystyrol mit makrocyclischen und offenkettigen Aminen führt zu Polymeren mit kovalenter Bindung über eine C—N-Verknüpfung. Die erhaltenen funktionalisierten Polymeren wurden hinsichtlich der Adsorption von Cu(II)-, Ni(II)- und Co(II)-Ionen aus wäßriger Lösung untersucht.
    Notes: Polymers containing moieties of amides covalently bound to highly crosslinked polystyrene by C—C connections were prepared via a polymer-bound malonic ester group in the reaction with open-chain diamines. The reaction of crosslinked, chloromethylated polystyrene with macrocyclic and open-chain amines results in covalent binding by C—N-connection. The synthesized functionalized polymers were investigated for uptake of Cu(II), Ni(II) and Co(II) ions from aqueous solutions.
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  • 61
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 1-6 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(phenylphosphindiylterephthaloyl), ein neues phosphorhaltiges Polymeres, wurde durch Lösungspolykondensation von Dilithium(phenyl)phosphin mit Terephthaloylchlorid bei niedriger Temperatur hergestellt. Es ist in polaren aprotischen Lösungsmitteln löslich; die inhärente Viskosität in DMF bei 30°C beträgt 19 ml/g. Das Polymere wurde mittels Elementaranalyse sowie IR- und 1H-NMR-Spektroskopie charakterisiert. TGA-Messungen ergeben, daß das Polymere in Luft bis 250°C stabil ist; es ist selbstverlöschend.
    Notes: Poly(phenylphosphinediylterephthaloyl), a novel phosphorus-containing polymer, was synthesized by low-temperature solution polycondensation of dilithio(phenyl)-phosphine with terephthaloyl chloride. The resulting polymer is soluble in polar aprotic solvents, having inherent viscosity of 19 ml/g in DMF at 30°C. The polymer was characterized by elemental analysis, IR and 1H-NMR spectroscopy. TGA data show that the polymer is stable up to 250°C in air. The polymer was found to be self-extinguishing.
    Additional Material: 3 Ill.
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  • 62
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine neue Methode für die Erweiterung des Meßbereiches der Ausschlußchromatographie, gekoppelt mit Lichtstreuung (SEC/LALLS), zu höherer molarer Masse, vorgestellt. Diese Methode nützt den Effekt, daß das Lichtstreusignal oft schon bei wesentlich kleineren Werten des Elutionsvolumens, also hoheren Werten der molaren Masse erfaßbar ist als das Konzentrationssignal und berücksichtigt dabei die Peakverbreiterung in der SEC. Das betreffende Rechenverfahren wird für den Fall einer logarithmischen Normalverteiung und einer wahrscheinlichsten Verteilung getestet. Im Falle von Polypropylen mit logarithmischer Normalverteilung (M̄W = 420 000 und M̄n = 99 000) kann der durch SEC/LALLS erfaßte Bereich der molaren Masse um einen Faktor von ca. 10 erweitert werden; bei einer wahrscheinlichsten Verteilung (M̄n = 100 000) liegt die erreichbare Erweiterung des Meßbereiches der molaren Masse beieinem Faktor von ca. 2.
    Notes: A new method for the extension of the measuring range of size exclusion chromatography coupled with light scattering (SEC/LALLS) to higher molar mass is presented. This method uses the fact that the light scattering signal can often be detected already at considerable smaller values of the elution volume (i. e. higher values of molar mass) than the concentration signal; furthermore, it takes into account the peak broadening effect in SEC. This procedure is tested for the case of a logarithmic normal distribution and a most probable distribution of molar mass. In the case of polypropylene with a logarithmic normal distribution (M̄w = 420 000, M̄n = 99 000), the range of molar mass covered by SEC/LALLS can be extended by a factor of about 10; with a most probable distribution (M̄n = 100 000), the attainable extension in molar mass assumes a factor of about 2.
    Additional Material: 2 Ill.
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  • 63
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 45-63 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Because of the interest in their possible application as biologically degradable polymers, the isotherms of sorption of water vapour by native and thermoplastic starch were measured. The thermomechanical treatment of starch and the insertion of glycerol as softener lead to the disappearance of the hysteresis and to the transition from a Type II to Type III isotherm. A theory, describing the sorption behaviour of swellable sorbents, is introduced and its statements are discussed by means of experimental results. The theory allows to draw conclusions on the molecular behaviour during sorption.
    Notes: Es wurden Wasserdampf-Sorptionsisothermen von nativer und thermoplastischer Stärke gemessen. Die thermisch-mechanische Behandlung der Stärke und das Einfähren von Glyzerin als Weichmacher fährt zum Verschwinden der Hysterese und zum Übergang von der Typ II in eine Typ III Isotherme. Eine Theorie, welche das Sorptionsverhalten von quellbaren Sorbentien gut beschreibt, wird kurz eingeführt und anhand der experimentellen Daten ihre Aussagen diskutiert. Die vorgestellte Theorie erlaubt wegen der physikalischen Bedeutung der Parameter Rückschlüsse auf die molekularen Vorgänge während der Sorption. Die Motivation zur Untersuchung des Sorptionsverhaltens von thermoplastischer Stärke ist deren möglicher Einsatz als biologisch abbaubarer Kunststoff.
    Additional Material: 7 Ill.
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  • 64
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In order to solve the problem of polymer swelling which limits the resolution of negative resists, we have developed new resists where the swelling does not appear. For our study, we developed resists including polymers containing the tetrathiafulvalenylcarbonyloxymethyl radical and dibromotetrachloroethane. In order to study the influence of the nature of the radical bearing the tetrathiafulvalene unit in the polymers on the microlithographic properties of these resists, we also studied polymers containing the tetrathiafulvalenylphenoxymethyl radical. The resists have been tested under UV irradiation. The dependence of resist sensitivity on molecular weight is reported.
    Notes: Pour résoudre le phéomène de gonflement qui limite la résolution des résines microlithographiques classiques, nous nous sommes intéressés à de nouvelles résines avec lesquelles ce phénomène n'apparait pas. Nous avons retenu pour notre étude les résines R qui renferment en mélange un polymère porteur de radicaux tétrathiafulvalénylcarbonyloxyméthyles et le dibromotétrachloroéthane. Afin de voir l'influence de la nature du radical porteur de l'unité tétrathiafulvalène dans le polymtrè sur les propriétés microlithographiques des résines R, nous nous sommes également intéressés aux polymères renfermant des radicaux tétrathiafulvalénylphénoxymethyles. Les résines R ont été testées sous irradiation UV. Leurs sensibilités dépendent en outre de la valeur de la masse molaire du polymèr.
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  • 65
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    Angewandte Makromolekulare Chemie 199 (1992), S. 33-44 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Hochfeste Polyethylen- (HSPE), Polypropylen- (PP), Polyethylenterephthalat-(PET) und Polyvinylalkohol-(PVA) Textilgarne wurden unter Anwendung des entwickelten kontinuierlichen Einweichprozesses mit verschiedenen funktionellen Monomeren, wie beispielsweise Acrylsäure (AA), Acrylamid (AM), Glycidylacrylat (GA) und 4-Vinylpyridin (VP) oberflächenfotogepfropft. Die Einfärbbarkeit der oberflächenmodifizierten Garne mit verschiedenen Textilfarbstoffen wurde untersucht. Im allgemeinen wurde eine erhebliche Verbesserung der Einfärbbarkeit beobachtet. Die Farbstoffaufnahme der oberflächenfotogepfropften Fasern wird von vielen Faktoren beeinflußt, beispielsweise von der Art der Faser, der Menge und den Eigenschaften des auf die Oberfläche der Fasern gepfropften funktionellen Monomeren, der Art des Textilfarbstoffs usw. Die Faseroberflächen, auf die ein Monomeres mit basischen Gruppen wie Acrylamid und 4-Vinylpyridin gepfropft wurde, lassen sich mit einem sauren Farbstoff wirkungsvoll einfärben. Dagegen läßt sich eine Faseroberfläche, auf die ein saures funktionelles Monomeres gepfropft wurde, leicht mit basischen Farbstoffen in tiefen Farbtönen einfärben. Die Farbstoffaufnahme steigt stetig mit zunehmender Pfropfung, in ESCA-Spectren als relative Intensitaten relevanter Linien gemessen. Die nicht gepfropften HSPE-, PP-, und PET-Fasern können mit bestimmten Farbstoffen in gewissem Maße eingefärbt werden. Bei der vorliegenden Arbeit erhöhte sich die Farbstoffaufnahme bei HSPE-Fasern, die mit GA gepfropft und mit dem Metallkomplexfarbstoff IO eingefärbt wurden, um das 3,4fache, bei PP-Fasern, die mit AA gepfropft und mit dem basischen Farbstoff MB eingefärbt wurden, um das 7,9fache, bei PET mit AM und dem Direktfarbstoff SL um das 6,1fache, bei PVA mit VP und dem sauren Farbstoff TE um das 15,3fache.
    Notes: High-strength polyethylene (HSPE), polypropylene (PP), poly(ethylene terephthalate) (PET), and poly(vinyl alcohol) (PVA) textile yarns have been surface-photografted with various functional monomers, such as acrylic acid (AA), acrylamide (AM), glycidyl acrylate (GA) and 4-vinyl pyridine (VP), by means of the continuous presoaking process developed. The dyeing of these surface-modified yarns with various textile dyes has been investigated. In general, considerable improvements of dyeability have been observed. The dye adsorption of the surface-photografted fibers is influenced by many factors, such as type of fiber, amount and properties of the functional monomer grafted on the surface of the fibers, type of textile dye, etc. The fibers surface-grafted with a monomer containing basic groups, such as acrylamide and 4-vinyl pyridine, are efficiently dyed with an acid dye. Conversely, a fiber surface-grafted with acidic functional monomer is easily dyed to deep shades with basic dyes. The dye adsorption increases monotonically with increasing grafting measured in ESCA spectra as relative intensities of relevant lines. The ungrafted HSPE, PP and PET fibers can be dyed to some extent with certain dyes. In the present work, the dye adsorption increased by 3.4 times for HSPE fiber grafted with GA and dyed with the metal complex dye IO, by 7.9 times for PP fiber grafted with AA and dyed with the basic dye MB, by 6.1 times for PET with AM and with the direct dye SL, and by about 15.3 times for PVA with VP and with the acid dye TE.
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  • 66
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 65-74 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die thermische Stabilität von Acrylnitril-Copolymeren wurde mittels DSC untersucht, um den Einfluß von halogenierten Comonomeren mit Carboxygruppen auf die Stabilisierung von PAN zu präfen. Es wird gezeigt, daß die Aktivierungsenergie fär die Cyclisierung des AN/Bromacrylsäure(BrAA)-Copolymeren (86,2 kJ/mol) deutlich niedriger als die der Copolymeren mit Chloracrylsäure (ClAA, 158 kJ/mol), Acrylsäure (AA, 128 kJ/mol) und Itaconsäure (IA, 102 kJ/mol) ist. Das erlaubt eine Stabilisierung bei häherer Temperatur und eine Verkürzung der Stabilisierungszeit. ClAA ist BrAA bezäglich der Stabilisierungseffektivität nicht überlegen. Der Mechanismus der Cyclisierung von AN-Copolymeren mit halogenierten, carboxygruppenhaltigen Comonomeren wird diskutiert.
    Notes: The thermal stability of AN copolymers was studied by DSC technique in order to get information on the influence of comonomers containing halogenated carboxylic acid on the stabilization of PAN. It is shown that the activation energy of cyclization is reduced in the case of the copolymer with bromoacrylic acid (BrAA, 86.2 kJ/mol) compared with chloroacrylic acid (ClAA, 158 kJ/mol), acrylic acid (AA, 128 kJ/mol) and itaconic acid (IA, 102 kJ/mol). Copolymer AN/BrAA permits the stabilization at higher temperature than AN/IA and AN/AA, helping to shorten the stabilization time. It is proved that comonomer ClAA is not superior to BrAA in the effectiveness of thermal stabilization. The mechanism of the cyclization reaction of AN copolymer containing halogenated carboxylic acid is discussed.
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  • 67
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 75-85 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden neue unsymmetrische cycloaliphatische Bisepoxyderivative hergestellt. Die unterschiedliche Reaktionsfahigkeit der zwei Oxiranringe (cycloaliphatisch und glycidylisch) gegenüber Carbonsäure wurde untersucht, wobei eine normale und anomale Ringöffnung der Glycidylgruppen beobachtet wurde. Eine Homopolymerisation des Oxirans wurde ebenfalls beobachtet. Mit Hilfe der 13C-NMR-Spektroskopie wurde die Struktur der Polymeren ermittelt. Die neuen Epoxidharze zeigen gute thermische Eigenschaften.
    Notes: New bisepoxy unsymmetrical cycloaliphatic derivatives have been synthesized. The different reactivity of both oxirane rings (cycloaliphatic and glycidylic) has been tested against carboxylic acids giving rise to normal and abnormal opening to the glycidyl group. Homopolymerization reaction was also observed. Polymer structures were identified by 13C-NMR spectroscopy. Thermal analysis carried out allowed to confirm their good thermal properties.
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  • 68
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 119-131 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: N,N′-4,4′-Diphenylmethane-bismaleimide (BMI) was oligomerized in semisolid phenolnovolak epoxide-resin (EP) up to P̄n = 10. The morphology of the novolakcured EP-BMI solid resins is a two-phase structure. It consists in a homogeneous EP-BMI phase of an interpenetrating polymer network (IPN) and a BMI phase. The dynamic-mechanical properties depend on the overall weight fraction w2 of BMI and on the degree of oligomerization (P̄)n of BMI. The relative shear modulus of the EP-EMI resin in the rubber state shows that both phases can be coherent. The glass transition temperature (Tg) can be correlated with the degree of oligomerization of the BMI, for instance Δ P̄n ≡ 10 corresponds to Δ Tg ≡ 35 K and Δ wx2 ≡ 0,25 (weight fraction of BMI in the homogeneous EP-BMI phase). Surprisingly, the breaking strength remains constant.
    Notes: N,N′-4,4′-Diphenylmethan-bismaleimid (BMI) wurde in halbfesten Phenolnovolak-Epoxidharzen (EP) bis P̄, = 10 oligomerisiert. Die novolakgehärteten EP-BMI-Festharze bilden eine Zweiphasenstruktur, bestehend aus einer EP-BMI-Mischphase der beiden sich durchdringenden Netzwerke (interpenetrating polymer network, IPN) und einer BMI-Phase. Die dynamisch-mechanischen Eigenschaften hängen vom Gesamt-BMI-Anteil w2 und vom Oligomerisierungsgrad P̄n des BMI ab. Der relative Schubmodul des EP-BMI-Harzes im kautschukelastischen Zustand zeigt, daß beide Phasen kohärent sein können. Die Glastemperatur Tg korreliert mit dem Oligomerisierungsgrad, z. B. entspricht ΔPn ≡ 10 einem ΔTg ≡ 35 K und einem BMI-Anteil Δ wx2 ≡ 0,25 in der Mischphase. Die Bruchzahigkeit bleibt unerwartet konstant.
    Additional Material: 8 Ill.
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  • 69
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Handelsübliche Araldit™-Polymere wurden mit Zimtsäure- bzw. Furanacrylsäurechlorid modifiziert und über [2 + 2]-Cycloaddition photochemisch vernetzt. Die Glasübergangstemperaturen der entstandenen Polymeren betragen bis zu 130°C bei Dielektrizitätskonstanten von ∊r = 3.0. Daher können diese Polymeren in Mehrlagenmikroverdrahtungen verwendet werden. Zahlreiche wohldefinierte, multifunktionelle Modifikatoren wurden synthetisiert und deren Einfluß auf die Polymerisation und die Eigenschaften der Araldit™-Polymeren eingehend untersucht.
    Notes: Commercially available Araldite™-type polymers have been modified with cinnamic and furan acrylic acid chlorides. The polymers were photochemically crosslinked via a [2 + 2] cycloaddition. The resulting polymers show glass transition temperatures up to 130°C and dielectrical constants of ∊r = 3.0. Therefore, these polymers can be applied as permanent resists in multi-layered wiring structures. Numerous well-defined multifunctional modifiers have been synthesized. The effect of those modifiers on the polymerization and properties of the araldite-type polymers has been studied in some detail.
    Additional Material: 1 Ill.
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  • 70
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 200 (1992), S. 61-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The photoinduced free radical crosslinking of silicone containing pendent acrylate or methacrylate groups was investigated by swelling measurements. A modified swelling test was applied to observe the network formation as a function of several parameters. The results show that the network density of the crosslinked polymers is a function of the light intensity, the exposure time, the acrylate content, the molecular weight of the uncrosslinked silicone acrylate and also of the length of the spacer group between the acrylate unit and the silicone backbone. Oxygen has only an influence on the polymerization kinetics, but it does not influence the network density.From the δB, -values of crosslinked silicone acrylates and silicone containing vinyl groups it is possible to analyze the structure of the network as a function of the olefinic group. The χ-parameters of both silicone types are of the same magnitude in the same concentration range.Kinetics investigations demonstrate that the order of the network formation is nearly unity. This result agrees with the polymerization kinetics.By means of swelling measurements it is also possible to study the influence of hydrogen siloxane additives as hydrogen transfer reagents.
    Notes: Die photoinduzierte radikalische Vernetzung von Siliconacrylaten bzw. -methacrylaten wurde mit Hilfe von Quellungsmessungen untersucht, wobei ein modifizierter Quellungstest erlaubt, die Netzwerkbildung als Funktion verschiedener Parameter zu betrachten. Die Ergebnisse zeigen, daß die Netzwerkdichte eine Funktion der Lichtintensität, der Bestrahlungszeit, des Acrylatgehalts, der Molmasse des unvernetzten Silicons und auch der Länge der Spacergruppe zwischen Acrylateinheit und dem Siliconrückgrat ist. Sauerstoff besitzt dagegen nur einen Einfluß auf die Polymerisationskinetik, nicht aber auf die Netzwerkdichte.Aus dem Vergleich der δB, -Werte der vernetzten Siliconacrylate und der vernetzten Vinylsilicone kann geschlossen werden, daß die Netzwerkstruktur auch vom Typ der olefinischen Gruppen abhängt. Die χ-Parameter besitzen jedoch im gleichen Konzentrationsbereich die gleiche Größe.Kinetische Untersuchungen zeigen, daß die Netzwerkbildung nach einem Zeitgesetz erster Ordnung verläuft. Dieses Ergebnis steht im Einklang mit der Polymerisationskinetik.Mit Hilfe der Quellexperimente ist es auch moglich, den Einfluß von H-Siloxanzusätzen als Wasserstoffüberträger zu untersuchen.
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  • 71
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 133-148 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The copolymerization of butadiene with a technical divinylbenzene fraction was investigated to study the modification of cis-1,4 polybutadiene. Beside the Ziegler-Natta-catalyst nickeloctanoate/bortrifluoride/aluminiumtriethyl, another catalytic system consisting of nickeloctanoate/titaniumtetrachloride/aluminiumtriethyl was used, which allows to polymerize more divinylbenzene because of its higher activity toward vinylaromates. With the help of spectroscopical, pyrolysis-gaschromatographical and thermoanalytical methods one can obtain relations between glass-, crystallization- and melting temperature and the microstructure of the polymer. It can be shown that not only the divinylbenzene but also the trans-1,4- and the 1,2-vinyl units are statistically distributed in the polymer. By this, beside the pyrolysis-gaschromatography, particularly the differential scanning calorimetry is a useful tool to characterize the structure of partially crosslinked polymers obtained from polymerization of technical fractions.
    Notes: Im Rahmen von Arbeiten zur Modifizierung des cis-1,6Polybutadiens wurde die Copolymerisation von Butadien und einer Divinylbenzolfraktion, insbesondere der Bereich mit kleinen Divinylbenzolgehalten, untersucht. Neben dem Ziegler-Natta-Katalysator Nickeloctanoat/Bortrifluoridetherat/Aluminiumtriethyl kam auch ein Nickeloctanoat/Titantetrachlorid/Aluminiumtriethyl-System zur Anwendung, welches es durch seine höhere Aktivität gegenüber Vinylaromaten ermöglicht, großere Mengen der Divinylbenzolfraktion zu polymerisieren. Durch die Anwendung von spektroskopischen, pyrolysegaschromatographischen und thermoanalytischen Charakterisierungsmethoden können Beziehungen zwischen den erhaltenen Glas-, Kristallisations- und Schmelztemperaturen und der Mikrostruktur des Polymeren hergestellt werden. Es zeigt sich, daß sowohl das Divinylbenzol als auch die trans-1,4 bzw. die 1,2-Vinyl-Einheiten statistisch in das Polymere eingebaut werden. Damit eignet sich neben der Pyrolysegaschromatographie besonders die Differential Scanning Calorimetry als eine einfache Methode zur Charakterisierung der Struktur von aus technischen Fraktionen erhaltenen und teilweise vernetzten Polymerproben.
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  • 72
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Optisch hochreine Gläser wurden aus Polystyrol (PS), Polymethylmethacrylat (PMMA) und statistischen Styrol-Methylmethacrylat-Copolymeren (S-MMA) hergestellt. Die an diesen Gläsern gemessene Lichtstreuung hängt von der chemischen Zusammensetzung des Polymeren und dem Brechungsindex des zugesetzten Weichmachers ab. Ein isorefraktiver Weichmacher verringert die Streuwerte der S-MMA-Copolymeren, hat aber keinen signifikanten Einfluß auf das Streuverhalten von PMMA. Ein Weichmacher mit einem vom Polymeren verschiedenen Brechungsindex verschlechtert die Streuwerte in allen untersuchten Fällen. Es wird gezeigt, daß ein isorefraktiver Weichmacher die Dämpfungseigenschaften von aus dem Copolymeren S-MMA 2/1 gezogenen polymeren Lichtleitern verbessert.
    Notes: High optical purity polystyrene (PS), poly(methyl methacrylate) (PMMA) and styrene-methyl methacrylate statistical copolymers (S-MMA) were prepared. Light scattering measured on polymeric glasses depends on the chemical composition of the polymer and on the refractive index of the plastifier added. An isorefractive plastifier reduces considerably the scattering values for the copolymers S-MMA, while having no significant effect on the scattering of PMMA. A plastifier with a refractive index different from that of the polymer raises distinctly the light scattering values in all cases. It has been shown that the isorefractive plastifier has a favourable effect on attenuation loss of polymeric optical fibers (POF) obtained from the copolymer S-MMA 2/1.
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  • 73
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: ABS/TPU- und SAN/TPU-blends were investigated on the basis of the analysis of viscoelastic behaviour of the components for characterization of the formation of morphology in melt mixing processes. Blends mixed in a laboratory kneeder and extruded from a high pressure capillary viscosimeter under definite conditions were characterized concerning their phase morphology by transmission electron microscopy. The types of morphology predicted by the help of rheological analysis could be confirmed by electron micrographs and quantitative analysis of morphology. It becomes evident, that the ratio of viscosity of the components has the primary influence on the formation of morphology in the blends. But also thermomechanically induced molecular destruction processes and thermodynamic interactions as well as connecting crystallisation conditions for the TPU-phase are not negligible with regard to resulting phase morphology.
    Notes: An ABS/TPU- bzw. SAN/TPU-Blends wurden Untersuchungen zur Morphologiebildung beim Schmelzemischen auf der Basis der Analyse des viskoelastischen Verhaltens der Komponenten angestellt. Unter definierten Bedingungen im Laborkneter gemischte und unter definierten Bedingungen mittels Hochdruckkapillarviskosimeter extrudierte Blendproben wurden hinsichtlich ihrer Phasenmorphologie elektronenmikroskopisch charakterisiert. Die mittels der rheologischen Analyse prognostizierten Morphologietypen und Morphologiebildungsmechanismen konnten anhand der elektronenmikroskopischen Aufnahmen und der quantitativen Morphologieanalyse bestätigt werden. Es zeigte sich, daß das Viskositätsverhältnis der Komponenten primären Einfluß auf die Morphologiebildung ausübt. Darüber hinaus sind auch thermomechanisch induzierte molekulare Abbauvorgänge und thermodynamische Wechselwirkungen sowie damit im Zusammenhang stehende Kristallisationsbedingungen für die TPU-Phase hinsichtlich der resultierenden Phasenmorphologie nicht zu vernachlässigen.
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  • 74
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Stabilität von Verbindungen von Polypropylen (PP) und Polycarbonat (PC) mit einem Acryl-Kleber wurde mit einer thermodynamischen, auf der Messung von Oberflächenspannungen beruhenden Methode bestimmt.Die Charakterisierung der Oberflächen zeigte, daß eine Plasmabehandlung die Bildung einer sauerstoffreichen Oberflächenschicht bewirkt. Eine Lagerung in Wasser führt bei PP zu keiner Veränderung dieser Schicht, während bei PC niedermolekulare, oxidierte Verbindungen ausgewaschen werden.Sowohl unbehandelte als auch mit Plasma behandelte PP-Verbindungen wiesen bei Lagerung in Wasser eine annehmbare Stabilität auf. Zwar wurde eine geringe Abnahme der Scherfestigkeit gemessen, aber unbehandeltes und plasmabehandeltes PP zeigten weiterhin adhäsives bzw. kohäsives Bruchverhalten.Im Falle von PC blieben nur die aus unbehandeltem PC hergestellten Verbindungen ausreichend stabil, während die aus plasmabehandeltem PC hergestellten Verbindungen stark abgebaut wurden. Bei den letzteren wanderte der Versagensort an die Polymer/Kleber-Grenzfläche, was auf die Ausbildung einer sehr hydrophilen, niedermolekularen Schicht zurückgeführt wird.
    Notes: The stability of PP and PC/acrylic adhesive joints has been assessed using a thermodynamic method based on surface tension components.Surface characterization showed that plasma treatment induces the formation of an oxygen-rich layer on treated surfaces. In the case of PP this layer does not change its composition upon immersion in water, while for PC leaching of oxidized species with low molecular weight was observed.Both untreated and plasma treated PP joints showed reasonable stability against immersion in water. A small reduction of shear strength was observed, but the fracture remained adhesive for untreated PP and cohesive for plasma treated PP.In the case of PC, only joints made from untreated PC showed fair sensitivity against immersion in water, while those made from plasma treated specimens degraded dramatically. In the latter case the locus of failure moved to the adhesive/adherend interface, the presence of a very hydrophilic, low molecular weight layer being suggested as responsible for this behavior.
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  • 75
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The chloromethylated polystyrenes bearing tetrathiafulvalenylcarbonyloxymethyl groups can be oxidized. We have shown that ion radical salts are obtained from these polymers and carbon tetrabromide after irradiation with UV light. Charge transfer complexes were prepared by mixing these polymers and 2,3-dichloro-5,6-dicyanobenzoquinone. The possible presence of sulfoxides as a result of oxidation of some tetrathiafulvalene units could explain the difficulties we have observed to filter solutions of these polymers.
    Notes: Les polystyrènes chlorométhylés renfermant des radicaux tétrathiafulvalénylcarbonyloxyméthyles peuvent être oxydés. Ainsi la formation de sels d'ions radicaux obtenus à partir de ces polymères et de tétrabromure de carbone, irradiés sous UV, a été mise en évidence. Des complexes de transfert de charge ont été préparés en mettant en présence ces polymères et de la 2,3-dichloro-5,6-dicyanobenzoquinone. La présence de sulfoxydes non décelés et résultant de l'oxydation de certaines unités de tetrathiafulvalène contenus dans ces polymères pourrait expliquer les problèmes rencontrés lors de la filtration de leurs solutions.
    Additional Material: 4 Ill.
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  • 76
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Metallkomplexierung von wasserloslichem Poly[1-(2-hydroxyethyl)aziridin-co-2-methyl-2-oxazolin] mit Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II) und Sr(II)-Ionen wurde in wäßriger Phase mit der Methode der Liquid-Phase Polymer-Based Retention (LPR) untersucht. Die Studie zeigt, daß alle Metallionen, außer Co(II) und Zn(II), bei pH 5 komplexiert wurden. Im Gegensatz zu Sr(II), das nur eine schwache Wechselwirkung in einem pH-Bereich von 3 bis 7 zeigte, wurden bei pH 7 94% Co(II) und 88% Zn(II) retentiert. Bei pH 3 zeigten nur Cu(II) und Cr(III) eine Wechselwirkung mit dem Polymeren, wobei die Retentionswerte 76% für Cu(II) und 52% für Cr(III) betrugen. Viskositätsmessungen des Copolymeren in Gegenwart von Metallionen wurden bei verschiedenen pH-Werten durchgeführt.
    Notes: The metal complexation of water-soluble poly[1-(2-hydroxyethyl)aziridine-co-2-methyl-2-oxazoline] with Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II), and Sr(II) ions was investigated in aqueous phase using Liquid-Phase Polymer-Based Retention (LPR). The study shows that all metal ions are complexed at pH 5, except Co(II) and Zn(II). In contrast to Sr(II), which showed only a slight interaction over a pH range of 3 to 7, 94% of Co(II) and 88% of Zn(II) were retained at pH 7. At pH 3, only Cu(II) and Cr(III) ions interacted with the copolymer with retention values of 76% for Cu(II) and 52% for Cr(III). Viscosimetric measurements of the copolymer were performed in the presence of metal ions at different pH values.
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  • 77
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 117-129 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Makroretikulare Copolymerperlen wurden durch Suspensionspolymerisation von Styrol, Bis(2-chlorethyl)vinylphosphonat (CEVP) und Divinylbenzol (DVB) in Gegenwart von Toluol als Verdünnungsmittel hergestellt. Die auf der Perlenoberfläche vorhandenen 2-Chlorethylphosphonat-Gruppen wurden durch Hydrolyse mit verdünnter Salpetersäure in Phosphon-Gruppen transformiert. Für die Einführung zusätzlicher Phosphon-Gruppen wurden die Copolymeren in Gegenwart von Aluminiumchlorid-Katalysator mit Phosphortrichlorid phosphoryliert, und die dabei entstandenen Dichlorphosphingruppen wurden mit verdünnter Salpetersäure verseift und oxidiert. Die Untersuchungen zur Chelatbildung der Copolymeren mit Metallionen zeigten, daß sie ein hohes Adsorptionsvermögen für Uranylionen und gute Stabilität gegen Chemikalien wie Säuren und Alkalien aufweisen. Es wurde auch gefunden, daß die Phosphongruppen enthaltenden Copolymeren recht effektive Adsorbentien für eine Vielzahl von Schwermetalionen wie Pb2+, Hg2+, Cd2+ und Cu2+ sind.
    Notes: Macroreticular copolymer beads were prepared by suspension polymerization of styrene, bis(2-chloroethyl) vinyl phosphonate (CEVP) and divinylbenzene (DVB) in the presence of toluene as diluent. The bis(2-chloroethyl) phosphonate groups on the bead surface were converted into phosphono groups by hydrolysis with dilute nitric acid. For the additional enrichment of phosphono groups, the copolymers were phosphorylated at the phenyl rings with phosphorus trichloride in the presence of aluminum chloride and hydrolyzed and oxidized with dilute nitrics acid. The investigations on metal ion chelation characteristics of the bead-type copolymers revealed that they have very high adsorptivity toward uranyl ions and good chemical resistance under acidic and alkaline media. It was also found that the phosphono group-containing copolymer beads are effective adsorbents for other heavy metal ions such as Pb2+, Hg2+, Cd2+, and Cu2+.
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  • 78
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    Angewandte Makromolekulare Chemie 197 (1992), S. 131-139 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Lösungen von Phenylisocyanat (I) in DMF wurden sowohl bei verschiedenen Temperaturen als auch in Gegenwart von Polyurethankatalysatoren und/oder 1,3-Diphenylharnstoff (II) gelagert. Die Reaktionsprodukte wurden mit Hilfe der HPLC quantifiziert. Neben der Hydrolyse von I zu II wird bei 20°C eine signifikante Reaktion von I mit II zu 1,3,5-Triphenylbiuret (III) beobachtet.Oberhalb 60°C reagiert I mit dem Lösungsmittel zu N,N-Dimethyl-N′-phenylformamidin (V). In DMF dissoziiert III bereits bei Temperaturen 〉 40°C zu I und II.
    Notes: Solutions of phenylisocyanate (I) in DMF were stored at different temperatures in the presence of both polyurethane catalysts and 1,3-diphenylurea (II). The reaction products were determined by HPLC. Beside the hydrolysis of I to II, a significant reaction of I with II to 1,3,5-triphenylbiuret (III) was observed at 20°C. Above 60°C, I reacted with the solvent to form N,N-dimethyl-N′-phenylformamidine (V). In DMF, III dissociated to I and II already at temperatures 〉40°C.
    Additional Material: 3 Ill.
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  • 79
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    Angewandte Makromolekulare Chemie 197 (1992), S. 141-147 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Glasfaserverstärkte Epoxidlaminate wurden aus den Matrixharzen Tetraglycidyldiaminodiphenylmethan (TGDDM) und Tetraglycidylbis(o-toluidino)methan (TGMBT) unter Verwendung von Härtern wie 4,4′-Diaminodiphenylmethan (DDM), 4,4′-Diaminodiphenylsulfon (DDS) und Diethylentriamin (DETA) hergestellt. Die mechanischen und dielektrischen Eigenschaften sowie die Chemikalienresistenz der Laminate wurden untersucht. Die Zugabe eines Epoxyverstärkers (20 Gew.-%, bezogen auf das Matrixharz) ergab eine Verbesserung der mechanischen Eigenschaften.
    Notes: Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane. (TGDDM) and tetraglycidyl bis(o-toluidino)-methaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane. (TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.
    Additional Material: 3 Tab.
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  • 80
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    Angewandte Makromolekulare Chemie 197 (1992), S. 149-157 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In 1 μm layers of different polymers containing 10 wt.-% 4,4′-diazidobiphenyl, the network formation under the influence of UV-irradiation was estimated by solvent treatment. The high activity of poly(glycidyl methacrylate) against the nitrenes formed is caused by its 1,2-epoxypropyl groups. As confirmed by IR-spectroscopy, the oxirane ring itself is not affected; NMR spectroscopic results indicate reactions between nitrenes and exocyclic CH2-groups.
    Notes: Die UV-Vernetzung in 1 μm-Schichten aus Polymeren verschiedener Konstitution, die 10 Gew.-% 4,4′-Diazidobiphenyl (DABP) enthalten, wird zeitabhängig anhand der reduzierten Schichtdicke nach Lösungsmittelbehandlung verglichen. Für die hohe Vernetzungsgeschwindigkeit von Polyglycidylmethacrylat mit den photolytisch gebildeten Bisnitrenen sind die 1,2-Epoxypropylgruppen verantwortlich. Der Oxiranring bleibt erhalten (IR-Spektroskopie). Wahrscheinlicher Reaktionsort ist die exocyclische CH2-Gruppe (13C-Festkörper-NMR-Spektroskopie).
    Additional Material: 4 Ill.
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  • 81
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    Angewandte Makromolekulare Chemie 197 (1992), S. 159-173 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ausgehend von 10 unterschiedlich 4′-substituierten 4-[N,N-dihydroxyethyl]aminoazobenzolen wurden durch Umsetzung mit Hexamethylendiisocyanat polymere Azofarbstoffe (M̄n 4200-10200) synthetisiert und die Substituentenabhängigkeit der spektralen Eigenschaften, der Redoxpotentiale und des Ausbleichverhaltens mit entsprechenden monomeren und dimeren Modellverbindungen verglichen. Die Ausbleichung erfolgt durch einen photooxidativen Prozeß. In der Reihenfolge monomerer 〉 dimerer 〉 polymerer Azofarbstoff sinkt die Lichtstabilität durch die Verringerung thermischer Desaktivierungsprozesse sowie durch einen möglichen intramolekularen Energietransfer.
    Notes: Starting from 10 different 4′-substituted 4-[N,N-dihydroxyethyl]aminoazobenzenes, polymeric urethane-azo dyes (M̄n 42000-10200) were prepared by reacting those with hexamethylene diisocyanate. The dependence of spectral properties, redox potentials and photofading behaviour on the kind of substitutents was determined and then compared with corresponding monomer and dimer model compounds. Photofading is caused by a photooxidative process. In the sequence of monomeric 〉 dimeric 〉 polymeric azo dyes, light stability decreases due to a diminution in thermal disactivation processes and in a possible intramolecular energy transfer.
    Additional Material: 3 Ill.
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  • 82
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    Angewandte Makromolekulare Chemie 197 (1992), S. 207-208 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 83
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    Angewandte Makromolekulare Chemie 197 (1992), S. 201-206 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bead cellulose, particle diameter 0.1 - 2.7 mm, was prepared from dispersions of viscose in chlorobenzene by applying the thermal sol-gel transition. Technical viscose containing modifiers Berol Visco 32, Berol Glyco 1540 and Kordamin V was used. The size of cellulose beads can be controlled by means of the amount of oleic acid in the dispersion medium. The optimal result was reached at 5 - 6 mg oleic acid in 90 ml chlorobenzene.
    Additional Material: 2 Ill.
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  • 84
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    Angewandte Makromolekulare Chemie 197 (1992), S. 185-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: PET- und PA 66-Textilien wurden unter normalen Bedingungen mit verschiedenen Dispersionsfarbstoffen gefärbt. Die gefärbten Textilien wurden mit 180 kV Elektronenstrahlung bestrahlt. Es wurde beobachtet, daß, verglichen mit den unbestrahlten Materialien, zunehmende Strahlungsdosen zu einer Zunahme des Gesamtfarbabstandes dE führten. Diese Farbunterschiede werden hauptsächlich von zwei Reaktionen verursacht: Erstens von der reversiblen Bildung von Farbstoffradikalen, die (an Luft) wieder zu den Ausgangsfarbstoffen reoxidiert werden können und zweitens durch die irreversible Reaktion von Farbstoffmolekülen mit dem Faserpolymeren. Die zweite Reaktion ruft eine permanente Farbänderung des Textils hervor, die bei entsprechenden Bestrahlungsbedingungen klein gehalten werden kann. Die Entscheidung, ob diese Veränderung toleriert werden kann, hängt von der weiteren Verwendung des Textils ab.
    Notes: PET and PA 66 fabrics were dyed with different disperse dyes under regular conditions. The dyed fabrics were irradiated with 180 kV electron radiation. It was observed that increasing radiation doses led to increasing total color differences dE if compared to the unirradiated materials.These color differences are mainly caused by two types of reactions. First by the reversible formation of dye radicals, which can be reoxidized (in air) to the original dye molecules, and second by the irreversible reaction of dye molecules with the fiber polymer. The latter reaction causes a permanent change of the color of the fabric, which can be kept low with the proper irradiation conditions. The decision whether or not this change can be tolerated depends on the further use of the textile.
    Additional Material: 12 Ill.
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  • 85
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    Angewandte Makromolekulare Chemie 197 (1992), S. 175-184 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Unterschiedlich 4′-substituierte 4-[N-Ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzole dienten als Ausgangsmonomere für Homopolymerisationen und Copolymerisationen mit Styrol und Methylmethacrylat. Die Photobleichung der erhaltenen polymeren Azofarbstoffe (M̄ 4200-9000) wurde mittels einer Xenotest-Apparatur untersucht und mit den entsprechenden Monomeren verglichen. Es wird angenommen, daß die in der Reihenfolge monomerer  -  copolymerisierter  -  homopolymerisierter Azofarbstoff sinkende Photostabilität durch zunehmenden Energietransfer in der Matrix verursacht wird.
    Notes: Different 4′-substituted 4-[N-ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzenes were used as starting monomers for homopolymerization and copolymerization reactions with styrene and methyl methacrylate. The photofading behaviour of the obtained polymeric azo dyes (M̄n 4200 - 9000) was investigated by means of a Xenotest device and compared with that of the corresponding monomers. The decreased photostability in the order monomer  -  copolymer  -  homopolymer was assumed to be caused by an increasing energy transfer in the matrix.
    Additional Material: 2 Ill.
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  • 86
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    Angewandte Makromolekulare Chemie 198 (1992), S. 31-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: N-Methacryloyloxyphthalimid und N-Methacryloyloxytetrabromphthalimid wurden durch Reaktion von Methacrylsäure bzw. Methacryloylchlorid mit N-Hydroxyphthalimid bzw. N-Hydroxytetrabromphthalimid hergestellt und homopolymerisiert. Die Austauschreaktionen der Polymeren mit Hydroxy- und Amin-Verbindungen wurden untersucht.
    Notes: N-Methacryloyloxyphthalimide (NMPI) and N-methacryloyloxytetrabromophthalimide (NMTPI) were prepared by the reaction of methacrylic acid with N-hydroxy-phthalimide and N-hydroxytetrabromophthalimide, respectively. The resulting monomers were polymerized. The reactions of the resulting polymers with hydroxy and amine compounds have been studied.
    Additional Material: 4 Tab.
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  • 87
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    Angewandte Makromolekulare Chemie 198 (1992), S. 15-29 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Tempern von Poly(etheretherketonketon) zwischen Glasübergangs- und Schmelztemperatur erzeugt normalerweise einen ausgeprägten Doppelschmelzpeak in der DSC-Kurve dieses Polymeren. Die eingehende Untersuchung dieses Doppelschmelzverhaltens in Abhängigkeit von Temperbedingungen und experimentellen Parametern zeigt, daß die Kristallisation als ein in zwei Stufen mit unterschiedlichen Zeitskalen ablaufender Prozeß beschrieben werden kann. Eine Rekristallisation als Ursache des Doppelpeaks kann widerlegt werden.
    Notes: Annealing poly(ether ether ketone ketone) (PEEKK) between glass transition and melting temperature generally results in a pronounced double peak melting behavior as obtained by DSC. Detailed investigations of the dependence of this double peak melting behavior on annealing conditions and experimental parameters clearly reveal that the crystallization can be described by a two-stage process occurring on different time scales. A recrystallization model as origin for the double peak melting curves can be disproved.
    Additional Material: 9 Ill.
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  • 88
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    Angewandte Makromolekulare Chemie 198 (1992), S. 1-14 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Nitrilkautschuk (NBR) wurde mit trans-Chlorcarbonylbis(tripheny1phosphin)rhodium(1) [trans-RhCI(CO)(PPh3)2] und Hydridocarbonyltris(triphenylphosphin)rhodium(1) [RhH (CO)(PPh3)3] als Katalysatoren in homogener Lösung selektiv hydroformyliert. Bei der Hydroformylierung von NBR mit 40 mol-% Acrylnitril bei 363 K, 5,6 MPa Gasdruck (CO:H2 = 1:1) und mit 0,43 mmol Katalysator werden mit trans-RhCl(CO)(PPh3)2 25% und mit RhH (CO)(PPh3)3 30% Umsatz erreicht. Beide Reaktionen sind bezüglich der Olefin- und Katalysatorkonzentration pseudo-erster Ordnung. Mit RhH (CO)(PPh3)3 wird eine höhere Reaktionsgeschwindigkeit erhalten. Die IR- und NMR-spektroskopische Charakterisierung der Produkte zeigt, daß sowohl die 1,4- als auch die 1,2-Butadieneinheiten hydroformyliert werden. Mit steigendem Aldehydgruppengehalt sinkt die Grenzviskositatszahl [q] und steigt die Glastemperatur. Bei hoheren Hydroformylierungsgraden wird Gelbildung beobachtet.
    Notes: Selective homogeneous catalytic hydroformylation of nitrile rubber (NBR) has been carried out in presence of trans-chlorocarbonylbis(triphenylphosphine)rhodium(I) [trans-RhCl(CO)(PPh3)3] and hydridocarbonyltris(triphenylphosphine)rhodium(I) [RhH(CO)(PPh3)3] as catalysts. At 363 K, under 5.6 MPa pressure (CO:H2 = 1:1) in presence of 0.43 mmol/l catalyst, the amount of hydroformylation is 25% in the case of trans-RhCl(CO)(PPh3)2 and 30% in the case of RhH (CO)(PPh3)3 for NBR with 40 mol-% acrylonitrile. Reaction kinetics suggest that both the reactions are pseudo-first order with respect to olefinic substrate and catalyst concentration. The rate of the reaction is higher in the case of RhH(CO)(PPh3)3. The characterization of the products by IR and NMR spectroscopy shows the formation of internal aldehyde groups from 1,4-units and terminal branched aldehyde groups from 1,2-units of the copolymer. Measurements on intrinsic viscosity [η] and glass transition temperature (Tg) suggest a decrease in [η] and an increase in Tg with the degree of formyl functionalization. Gel formation has been observed at higher degree of hydroformylation.
    Additional Material: 7 Ill.
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  • 89
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    Angewandte Makromolekulare Chemie 198 (1992), S. 61-70 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Komplexierung von Rhenium in einer polymeren Methacrylat-Matrix mit funktionellen Diethylentriaminpentaessigsäure-Gruppen wurde untersucht. Es werden diamagnetische Komplexe gebildet, wobei Rhenium in einer heterogenen Koordinationssphäre gebunden wird, bestehend aus Chlor und mehrfach gebundenem Sauerstoffsowie Carboxygruppen, die als einzige funktionelle Gruppe des polymeren Trägers als Ligand des Metallatoms wirken. Die Rhenium-Komplexe wurden durch IR- und UV-VIS-Spektroskopie sowie durch Messung ihrer magnetischen Momente charakterisiert.
    Notes: The bonding of rhenium to diethylenetriaminepentaacetic acid functional groups of a polymeric methacrylate matrix was studied. Diamagnetic complexes were formed of Re(V) with the heterogeneous coordination sphere containing atoms of chlorine and multiply bonded oxygen in addition to carboxylic groups, which are the only groups of the polymeric support functioning as ligands in the bonding to the metal. The rhenium complexes were examined by IR and UV-VIS spectroscopy and by magnetic moment measurements.
    Additional Material: 1 Ill.
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  • 90
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    Angewandte Makromolekulare Chemie 198 (1992), S. 51-60 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Meta-halogenierte Phenole sind bekanntermaßen chemisch und thermisch stabiler als ihre ortho- oder para-halogenierten Analoga. Die Verwendung eines reaktiven Zwischenproduktes, hergestellt durch Bromierung von 2,4,6-Trimethylphenol, als Alkylierungsmittel für den Einbau der stabilen m-Bromphenol-Einheit in verschiedene organische Substanzen und Polymere wird beschrieben. Bei der Anwendung als Verkapselungsmaterialien für elektronische Bauteile zeigten sich Epoxid-Derivate von Novolaken mit m-Bromphenol-Einheiten bezüglich hydrolytischer und thermischer Stabilität den konventionellen Tetrabrombisphenol-A-Epoxidharzen, die ortho- und para-bromiert sind, überlegen. Die m-Bromphenolgruppe verbessert die Bauteilzuverlässigkeit bei gleichzeitiger Erfüllung der Anforderungen an das Brandverhalten.
    Notes: Meta-halogenated phenols are generally known to be more chemically and thermally stable than their ortho- or para-halogenated counterparts. A reactive intermediate, produced by the bromination of 2,4,6-trimethylphenol is being used as an alkylating agent to incorporate this stable m-bromophenol moiety into varieties of organic compounds and polymers. In electronic encapsulation applications, epoxy derivatives of novolacs containing m-bromophenol have exhibited superior hydrolytic and thermal stability as compared with the conventional tetrabromo bisphenol-A epoxies which are ortho-brominated phenolics. The m-bromophenol moiety contributes to the extended device reliability while meeting flame retardency requirements as well.
    Additional Material: 5 Tab.
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  • 91
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Additionspolymere aus Bisphenol-A und Epichlorhydrin lassen sich mit Arylacryloylchloriden verestern. Die gebildeten Photoresists können mit UV-Licht (λ ≥ 280 nm) gehärtet werden. Aus FT-IR Messungen ergibt sich, daß die Netzwerkbildungsreaktion einem Zeitgesetz zweiter Ordnung gehorcht. DSC- und TGA-Messungen wurden durchgeführt. Die photovernetzten Polymeren weisen Glastemperaturen bis zu 171 °C auf und sind bis mindestens 350 °C thermisch stabil. Spektroskopische Daten werden aufgeführt.
    Notes: Addition polymers of bisphenol-A and epichlorohydrin can easily be esterified with aryl acryloyl chlorides to yield photosensitive polymers. The photoresists are curable with UV-irradiation (λ ≥ 280 nm). FT-IR measurements indicate that the network formation fonforms to second order kinetics. DSC and TGA measurements were carried out. The glass transition temperature of irradiated material is up to 171oC; the material is thermally stable up to 350oC. Spectral data are given.
    Additional Material: 2 Ill.
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  • 92
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    Angewandte Makromolekulare Chemie 198 (1992), S. 39-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine Ultraschall-Meßmethode vorgestellt, mit der sich fünf voneinander unäbhangige Elästizitatskonstanten von uniaxial symmetrischem Material bestimmen lassen. Für die Messung werden nur fünf Ultraschallausbreitungsgeschwindigkeiten benötigt. Vermessen wurden spritzgegossene Composite aus Polyphenylensulfid, Polyarylethersulfon mit Cardo-Seitengruppen, kurzen Kohlefasern und RUB. Die Ergebnisse zeigen eine enge Beziehung zwischen den elastischen Eigenschaften und der Struktur der Materialien auf.
    Notes: The paper makes an approach to the determination of the five independent elastic constants of uniaxial symmetric material with the ultrasonic immersion technique. Only five ultrasonic wave velocities are required during measurement. The elastic constants of the moulded composites comprised of poly(phenylene sulfide), poly(aryl ether sulfone) with cardo side groups, short carbon fiber and carbon black are measured by using the suggested treatment. The results exhibit a close relationship between the elastic properties and the structure of the materials.
    Additional Material: 6 Ill.
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  • 93
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    Angewandte Makromolekulare Chemie 198 (1992), S. 83-89 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Membranen aus interpenetrierenden Netzwerken (IPN) wurden auf ihre Eignung für die Anwendung als Piezodialyse-Membranen untersucht. Bei diesen IPN-Membrane? handelt es sich nicht um Mosaik-Membranen. Bei zwei der IPN-Membranen enthielten die Permeate eine höhere NaCl-Konzentration als die Ausgangslösung (differentialrefraktometrisch bestimmt). Für eine dieser Membranen wurden die Salzgehalte auchtitrimetrisch mit AgNO3 ermittelt; die Ergebnisse belegen den positiven Piezodialyse-Effekt.
    Notes: In the present study, interpenetrating polymer network (IPN) membranes were investigated for their potential application as piezodialysis membranes. These IPN membranes are not mosaic membranes. It was found that some of these membranes did show piezodialysis effects. Two of the membranes tested under high pressure gave permeates which were found to be more concentrated in sodium chloride than the initial feed solution, when analyzed by differential refractometry. The permeates from one membrane were double checked by titrating the chloride ion with silver nitrate solution. The results of the titration also indicated a positive effect.
    Additional Material: 1 Ill.
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  • 94
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    Angewandte Makromolekulare Chemie 198 (1992), S. 91-110 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden Untersuchungen zum Flüssig-Dampf- und Flüssig-Fliissig-Gleichgewicht in Mischungen aus den Monomeren Ethen, 1-Buten, 4-Methyl-1 -penten und einem Polyethylenwachs bei mittleren Drücken durchgeführt. Auf der Basis der Chain-of-Rotators (COR) Zustandsgleichung, die mit einem Gruppenbeitragsmodell modifiziert wurde, wurden die Phasendiagramme der binaren und ternären Subsysteme sowie für das quaternare Gesamtsystem berechnet. Die Berechnungen ergeben eine zufriedenstellende Beschreibung des Flussig-Dampf-Gleichgewichtes und dessen Überlappung mit einem Flüssig-Flussig-Gleichgewicht bei höheren Drücken und Temperaturen. Die Mischungslücken in den beiden Systemen aus dem Polyethylenwachs mit 1 -Buten bzw. 4-Methyl-1 -penten werden auch nach Zugabe von Ethen zu den binären Mischungen beobachtet. Die Berechnungen zeigen ein kleines Dreiphasengebiet in allen entsprechenden ternären Mischungen. Eine Flüssig-Flüssig-Mischungslücke, die das Flüssig-Dampf-Gebiet schneidet, wird auch im quäternaren Gesamtsystem durch die Berechnungen mit dem modifizierten COR-Model1 gefunden. Diese doch überraschend komplizierten Phasenverhältnisse rnüssen bei der Abscheidung der Monomeren nach dem Syntheseschritt ausreichend beachtet werden.
    Notes: Some measurements of the vapour-liquid and/or the demixing equilibrium at moderate pressures were carried out in systems containing the monomers ethene, 1-butene, 4-methyl-1-pentene and a polyethylene wax. A group-contribution-modified chain-of-rotators (COR) equation of state was used to calculate the phase diagrams in all binary and ternary subsystems and in the whole quarternary mixture. The calculations lead to a satisfying description of the vapour-liquid equilibrium and its intersection by a liquid-liquid region at higher pressures and temperatures. The miscibility gaps in both mixtures of the polyethylene wax with 1-butene and 4-methyl-1-pentene, respectively, were observed again after adding ethene to these binary mixtures. The calculations indicate a small three phase triangle in all corresponding ternary mixtures. A liquid-liquid demixing region intersecting the vapour-liquid surface could also be found in the whole quaternary system by calculation with the modified COR model. This surprisingly complicated phase behaviour has properly to be taken into account during the separation of the monomers after the co- or terpolymerization process.
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  • 95
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 111-122 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Optisch aktives (+)-2-endo-Acetoxy-5-endo-bornylmethacrylat (ABMA) wurde aus (+)-Campher hergestellt und in Benzol radikalisch homo- bzw. mit achiralem Methyl-methacrylat (MMA) bzw. Styrol (St) copolymerisiert. Der EinfluB von Temperatur und Reaktionszeit auf den Polymerisationsverlauf wird diskutiert. Die Copolymerisations-parameter (r1 und r2, nach Fineman-Ross) für Poly(ABMA-co-MMA) und Poly(ABMA-co-St) sowie die Q- und e-Werte für ABMA wurden berechnet.Der Absolutwert der spezifischen Drehung von Poly(ABMA-co-MMA) nimmt mit steigendem ABMA-Gehalt im Copolymeren zu. Eine geringe Abweichung von der Linearität deutet darauf hin, daß die Copolymerhauptkette nicht asymmetrisch ist. Aus der Temperatur- und Löjsungsmittelabhangigkeit der spezifischen Drehung der beschriebenen Homo- und Copolymeren laßt sich schlierjen, daß diese nicht in einer speziellen helikalen Konformation vorliegen. Die Eignung der chiralen Polymeren als Katalysatoren für die asymmetrische Addition von Butyllithium an verschiedene Aldehyde in Abhängigkeit von der Temperatur wurde untersucht.
    Notes: Optically active (+)-2-endo-acetoxy-5-endo-bornyl methacrylate (ABMA) was prepared from (+)-camphor. The free-radical homopolymerization of ABMA and its copolymerization with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2′-azoisobutyronitrile in benzene. Effects of temperature and reaction time on the copolymerization were discussed. The monomer reactivity ratios (r1, r2) for poly(ABMA-co-MMA) and poly(ABMA-co-St) as well as Q and e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. It was found that the absolute value of the specific rotation of poly(ABMA-co-MMA) increased with increasing ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of n-butyllithium to aldehydes were investigated. The effect of temperature and aldehydes on the asymmetric addition were also discussed.
    Additional Material: 6 Ill.
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  • 96
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Verschiedene α-oxoethylierte und α-hydroxyethylierte Styrol-Divinylbenzol-Copolymere (St-DVB) mit Unterschieden in Vernetzungsgrad und Porosität wurden hergestellt und auf ihre Eignung als Adsorbentien für ein nichtionisches Detergens (Nonaethylenglycol-mono-nonylphenylether) untersucht. Die durch Einführung der α-Hydroxy-ethylgruppen erreichte Verbesserung der Adsorptionskapazität war in den wenig vernetzten Harzen beträchtlich. Die mit 10 Vo1.-% DVB in Gegenwart von 100-120 Vo1.-% 2,2,4-Trimethylpentan hergestellten α-hydroxyethylierten Harze wiesen das höchste Adsorptionsvermögen auf, das sowohl von der Makroporosität als auch der Gelporosität abhängt. Die Anwendung der Harze als Säulenmaterial wurde geprüft und ihre Adsorptionseigenschaft als “Durchbruch”-Kapazität ermittelt.
    Notes: Several α-oxoethylated and α-hydroxyethylated styrene-divinylbenzene (St-DVB) resins having different degrees of crosslinking and porosity were prepared and their adsorption behaviour toward a nonionic surfactant, decaethyleneglycol nonylphenyl monoether, was investigated. The increment of the adsorption capacity caused by the introduction of the α-hydroxyethyl groups was remarkable in the less crosslinked resin. The α-hydroxyethylated resin derived from the St-DVB resin synthesized with 10 vol.-% DVB and 100 - 120 vol.-% of 2,2,4-trimethylpentane showed the highest capacity among the resins tested. The significance of both macroporosity and gel porosity in the effective adsorption of the nonionic surfactant was elucidated. A column operation using proposed resins was carried out and versatility was evaluated in terms of the breakthrough capacity.
    Additional Material: 7 Ill.
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  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 201 (1992), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Pigmentdispersion in unter verschiedenen Bedingungen extrudiertem Polyethylen hoher Dichte wurde mit einem an ein computergesteuertes Dunkelfeldmikroskop gekoppeltes Mikrophotometer quantitativ bestimmt. Mit dieser Methode lassen sich durch geringe Änderungen der Verarbeitungsbedingungen hervorgerufene Unterschiede in der Dispergiergüte feststellen. Da die Meßapparatur vergleichsweise preiswert ist, ist dieses Verfahren besonders für Kleinmengenverarbeiter interessant.
    Notes: A microphotometer attached to a computer-controlled darkfield microscopy system has been used for the quantitative measurement of the degree of pigment dispersion in high-density polyethylene extruded at specified varying processing conditions. The method distinguishes levels of pigment dispersion in extrudates obtained from subtle changes in processing conditions. Since the set-up is comparatively inexpensive, the technique promises to be particularly useful to small-scale manufacturers.
    Additional Material: 8 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 201 (1992), S. 23-31 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Mechanik des elastoplastischen Bruchs wurde auf eine Reihe von Probekörpern aus EPDM-modifiziertem Polyamid 6 mit unterschiedlichem EPDM-Gehalt angewandt, um ihr Bruchverhalten einwandfrei zu charakterisieren. Insbesondere wurde das Integral JR gemessen, um die Festigkeit JIC am Ursprung des Bruchs sowie den Ausbreitungsparameter dJ/da abzuleiten. Die erzielten Ergebnisse werden auf ihre Abhängigkeit von Gummigehalt, Temperatur und Verformungsgeschwindigkeit untersucht und diskutiert.
    Notes: Elasto-plastic fracture mechanics has been applied to a series of EPDM-modified polyamide-6 samples with varying rubber content, in order to characterize properly their fracture behaviour. J-testing has been carried out to determine the J-resistance (JR) curve and to evaluate therefrom the fracture initiation resistance, JIC, and the fracture propagation parameter dJ/da. The results obtained are analyzed and discussed as a function of rubber content, temperature, and strain rate.
    Additional Material: 6 Ill.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 200 (1992), S. 201-201 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 201 (1992), S. 11-21 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The kinetics of the polycondensation of Na2S · 3H2O and 1,4-dichlorobenzene to poly(phenylene sulfide) in 1-methyl-2-pyrrolidone as solvent was studied in a differential scanning calorimeter at temperatures from 220°C to 260°C. Stainless steel high-pressure capsules of 30 μl volume were used as micro reactors.The reaction is highly exothermic. At 220°C the enthalpy of reaction reaches a value of 180 kJ/mol. The polycondensation is characterized by an autocatalytic behaviour. The kinetics can be modelled by a second order equation with respect to the stoichiometrically charged monomers and a propagation rate constant being dependent on conversion. The activation energy of the polycondensation is 95 kJ/mol.
    Notes: Die Polykondensation von Na2S·3H2O und 1,4-Dichlorbenzol im Lösungsmittel 1 -Methyl-2-pyrrolidon wurde in kleinen Hochdruck-Kapseln aus Edelstahl mit einem Volumen von ca. 30 μl in einem Differentialkalorimeter im Temperaturbereich von 220°C bis 260°C kinetisch untersucht. Die Reaktion ist stark exotherm, bei 220°C beträgt die Reaktionsenthalpie ca. 180 kJ mol-1. Sie ist durch ein autokatalytisches Verhalten gekennzeichnet, welches mit einem Zeitgesetz 2. Ordnung in bezug auf die Konzentration der stöchiometrisch eingesetzten Monomeren und einer vom Umsatz abhängigen Reaktionsgeschwindigkeitskonstante des Kettenwachstums beschrieben werden kann. Die Aktivierungsenergie beträgt 95 kJ mol-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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