Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high‐resolution nuclear magnetic resonance spectroscopy

The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in ¹H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006     

The effect of fluorine-based plasma treatment on morphology and chemical surface composition of biocompatible silicone elastomer

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) have been used to investigate the effect of reactive ion etching (RIE) on poly(methylhydrogensiloxane-co-dimethylsiloxane) surface in fluorine-based plasmas. Polysiloxane layers supported on the standard silicon wafers were etched using SF₆ + O₂ or CF₄ + O₂ plasmas. SEM studies show that the polysiloxane morphology depends on plasma chemical composition strongly. Presence of a columnar layer likely covered with a fluorine rich compound was found on the elastomer surface after the CF₄ + O₂ plasma exposure. After the SF₆ + O₂ or CF₄ + O₂ plasma treatment the polysiloxane surface enriches with fluorine or with fluorine and aluminum, respectively. Different morphologies and surface chemical compositions of the silicone elastomer etched in both plasmas indicate different etching mechanisms.     

Filament sets and homogeneous continua

New tools are introduced for the study of homogeneous continua. The subcontinua of a given continuum are classified into three types: filament, non-filament, and ample, with ample being a subcategory of non-filament. The richness of the collection of ample subcontinua of a homogeneous continuum reflects where the space lies in the gradation from being locally connected at one extreme to indecomposable at another. Applications are given to the general theory of homogeneous continua and their hyperspaces.     

At the other side of a saddle-node

We describe phenomena occurring just before a saddle-node bifurcation for one-parameter families of interval maps. In particular, as a parameter approaches the bifurcation value, attracting periodic orbits of periodsk, k+1,k+2,k+3,... can appear. We make a detailed study of a family of cusp-shaped maps, where this phenomenon occurs in a pure form.     

Plane contact problems for a periodic two-layered elastic composite

Summary This paper deals with the two-dimensional static punch problems in the presence of friction for a periodically layered half-space. Within the framework of the homogenized model of linear elasticity with microlocal parameters [8–11] the exact solutions of the considered problems are obtained. The case of the indentation of the composite body by a rigid rectangular punch has been discussed in detail.

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Ebene Kontaktprobleme für ein periodisches elastisches Zweischichten-Komposit

Übersicht In dieser Arbeit wird das zweidimensionale statische Stempelproblem mit Reibung für einen periodisch geschichteten Halbraum betrachtet. Im Rahmen eines Homogenisierungsmodells der linearen Elastizitätstheorie mit mikropolaren Parametern werden die exakten Lösungen der betrachteten Probleme gewonnen. Im Detail wird das Eindringen eines rechteckigen starren Stempels behandelt.

     

Intra- versus intermolecular hydrogen bonds in salicylamide derivatives

The crystal structures, solid-state infrared patterns, and thermal properties of two polymorphs of 4-nitrosalicylanilide are presented. In both polymorphs, intramolecular hydrogen bonds are found between the phenol oxygen and the amide proton, and intermolecular hydrogen bonds are found between the amide carbonyl oxygen and the phenol proton. These hydrogen bond patterns are compared to those found in other known salicylamide derivatives and an analysis is given of the factors contributing to preferences for intra- or intermolecular hydrogen bonds in these structures. Crystal data: polymorph, orthorhombic,Pbca,a=11.003(4),b=27.959(7),c=7.622(5) Å,Z=4,V=2345(3) ų, andR=0.038 (1351 reflections); polymorph, monoclinic,P2₁/a,a=28.36(1),b=11.64(1),c=7.293(8) Å,=90.68(6)°,Z=8,V=2408 ų, andR=0.043 (2425 reflections).     

Some aspects of deformation in Al-Zn alloys

Creep resistance investigations of the Al-40 wt % Zn alloy at room temperature have been performed and revealed some creep compliance. Additions of Cu and Si decrease considerably the preliminary creep compliance in the alloy which then turn to be dimensionally stable and resistant to creep. Tensile test investigations performed at different deformation rates have not revealed the existance of the superplastic deformation mechanism.Presented at the 4^th International Symposium on Plasticity of Metals and Alloys, September 711, 1987, Srni, Czechoslovakia.