Degradation on freezing dilute polystyrene solutions in p-xylene

Chain scission was observed during the crystallization of p-xylene in dilute polystyrene solutions. Degradation yields were determined by gel permeation chromatography, as a function of the number of freeze-and-thaw cycles, polymer concentration, and initial polymer molecular weight (M). The rate constant for chain scission K_c increases with the polymer chain length, from 0.021%/cycle at M = 110·10³ to 4.7%/cycle at M = 8.5·10⁶. Over the two decades range of investigated molecular weights, K_c follows an empirical scaling law of the form K_c ～ (M ? M_lim)^1.17578, where M_lim is a limiting molecular weight ? 29,000 g. mol^?1 below which no degradation could be induced. Some propensity for midchain scission was detected, although this tendency was much weaker in comparison to flow-induced degradation. A chain scission model based on crack propagation failed to reproduce the experimental results. To explain the observed dependence of K_c with the square of the radius of gyration, an interfacial stress transmission mechanism between the crystallization fronts and the polymer coil has been proposed. © 1994 John Wiley & Sons, Inc.     

Microdeformation in thin films of 3FDA/PMDA polyimide and polyimide nanofoams

Transmission electron microscopy has been used to investigate the microdeformation behavior of thermally imidized thermoplastic pyromellitic dianhydride/1,1-bis(4-amino-phenyl)-1-phenyl-2,2,2 trifluoroethylene (3FDA/PMDA) polyimide films with a T_g of ～ 440°C, prepared by solution casting of a polyamic ester precursor. Failure of the films at room temperature was by unstable cracking at about 5% strain, accompanied by homogeneous shear deformation at the crack tips. As the temperature was raised to above 100°C, zones of mixed shear and crazing were observed, and a stick-slip mode of cracking. Above about 300°C shear was once again the dominant deformation mechanism and the films became fully ductile. In films containing porosity on a scale of a few nanometers, prepared by thermal degradation/imidization of a 3FDA/PMDA/poly α-methyl styrene graft copolymer, film failure at room temperature was also by unstable cracking, but a zone of multiple craze-like features was observed at crack tips, rather than a single shear deformation zone. The increase in extent of this zone of craze-like features as the temperature was raised was again associated with an increase in crack stability. ©1995 John Wiley & Sons, Inc.     

KINETICS AND PHASE TRANSFORMATIONS DURING THE REACTION OF NaCl-SODALITE IN AMMONIUM CHLORIDE SOLUTIONS

The reaction behavior of sodium chloride sodalite Na₈[AlSiO₄]₆Cl₂ in ammonium chloride solution has been investigated under mild hydrothermal conditions (T = 473 K) for reaction times up to 72 h. Reactions under weak acid conditions led to an amorphous aluminosilicate phase comparable to a leaching process. This material forms an amorphous layer around the sodalite grains, preventing the framework from further decomposition. About 52% of sodalite was damaged by acid leaching after 11 hours and this amount remains nearly constant even at longer reaction periods up to 72 hours. Cation exchange was observed in sodalite only on a very low level (< 10%). Beside these reactions under acid conditions (pH » 5) some additional experiments in alkaline solutions were done to improve ion exchange of sodalite. Thus an ammonium/ammonia buffer solution was used (pH » 9) at various temperatures in a range of 353 – 473 K. Neither cation exchange nor decomposition of the sodalite was obtained at 353 and 393 K after 72 hours. Formation of amorphous material started at 433 K. In contrast to the acid conditions a total transformation of sodalite into a crystalline ammonium aluminosilicate phase was observed at 473 K.     

Die Rolle der Kettenverschlaufungen bei der Ausheilung von Brüchen

Zusammenfassung Bei der Ausheilung von Brüchen in thermoplastischen Polymeren spielen der Grenzflächenkontakt, gegebenenfalls die Durchmischung während erzwungener Fließprozesse, vor allem jedoch die Interdiffusion eine Rolle. In dieser Arbeit wird eine kurze Übersicht über Untersuchungen der ersten beiden Phänomene gegeben. Ausführlicher wird dann auf bruchmechanische Untersuchungen der Grenzflächenfestigkeit (G _c ) eingegangen. Die Beobachtung, daßG _c mit der Quadratwurzel aus der Ausheilzeitt _p zunimmt, läßt sich durch ein Diffusionsmodell der Bildung von Kettenverschlaufungen erklären. Die Aktivierungsenergie des Diffusionsprozesses wurde für PMMA und SAN direkt (zu 274 kJ mol^–1) bestimmt, die Diffusionskonstante und die mittlere Eindringtiefe (2 bis 3 nm) der Molekülknäuel über die Grenzfläche hinweg aus einem Reptationsmodell berechnet. Infrarotspektroskopische Messungen der Interdiffusion von SAN in PMMA führen zu vergleichbaren Diffusionskonstanten.

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Summary The (re)healing of cracks in thermoplastic polymers depends on the interfacial contact, in some cases on the exchange of matter during forced flow processes, and, in particular, on the interdiffusion of molecules. In this paper a short review on investigations of the first two phenomena will be given. Fracture mechanics studies of the interfacial strength (G _c ) will then be dealt with more extensively. The observation thatG _c increases with the square root of the healing timet _p is explained by a diffusion model of entanglement formation. The energy of activation of the diffusion process has been determined directly for PMMA and SAN (to be 274 kJ mol^–1), the diffusion constant and the average depth of interpenetration (2 to 3 nm) of the molecular coils across the interface have been calculated from a reptation model. The infrared spectroscopic determination of the interdiffusion of SAN in PMMA leads to comparable diffusion constants.

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Résumé La cicatrisation des fissures dans les thermoplastes dépend du contact interfacial, le cas échéant d'un échange de matière dans le processus de fluage, mais surtout de l'inter diffusion des macromolécules. Cet article donne un bref résumé des deux premiers phénomènes. Les mesures de la résistance interfaciale,G _c , par la mécanique de rupture seront ensuite discutées de manière approfondie. L'observation queG _c augmente avec la racine carrée du temps de cicatrisation,t _p , est expliquée par un modèle de formation des enchevêtrements par diffusion. L'énergie d'activation pour la diffusion a été déterminée directement pour le PMMA et le SAN (274 kJ mol^–1), la constante de diffusion et la distance moyenne d'interpénétration (2 à 3 nm) ont été calculées sur la base d'un modèle de reptation. La mesure de l'interdiffusion du SAN en PMMA par spectroscopie infrarouge donne des constantes de diffusion comparables à celles qui ont été calculées.

     

Elastic interaction between linear polymeric chains and periodic potentials

The elastic displacement of an axially stressed chain within crystalline surroundings, which was first treated by Chevychelov, is reexamined. We compare the results obtained for homogeneously distributed masses with that for discrete atoms, considering the nonuniformity of the potential of a crystal containing hydrogen bonds. In polyethylene and polyamide the maximum mechanical excitation of a chain penetrates into the crystal a distance of 15 to 20 chain atoms. The effect of the relative position of the crystal boundary on the stress-strain field was studied and the energy of defects calculated.     

Isotropic proton-density-weighted high-resolution MRI for volume measurement of reconstructed orbital fractures--a comparison with multislice CT

Objective

The cause of enophthalmos as a late complication after orbital reconstruction is poorly investigated. Multislice CT (MSCT) is usually employed for its assessment, in spite of limitations regarding soft tissue depiction/imaging, as well as the implication of radiation and production of artifacts. Magnetic resonance imaging (MRI) has been shown to be a valuable alternative. The aim of this study was to establish a bony and soft tissue orbital volume calculation method based on different high-resolution MRI sequences compared to MSCT.

Materials and Methods

Thirty-seven patients were included in this prospective study investigating the origin of enophthalmos present 3–4 months after complex orbital reconstruction. Morphological and dimensional changes of the orbit, eye globes, extraocular muscles and fat content were investigated 3–4 months after surgery. To assess the site and size of bony and soft tissue changes in the traumatized orbits, we used MSCT and MR images as well as corresponding 3-D reconstructions.

Results

All enophthalmic orbits revealed a significant bony volume increase compared to the contralateral side as well as a reduced sagittal eye projection. Mean orbital volume enlargements of 1.0 cm³ lead to 0.93 mm enophthalmos (P<.05). Hardly any fatty atrophy could be depicted by the different MRI techniques.

Conclusions

For soft tissue depiction of the orbit, MRI was superior to MSCT. Particularly, proton density weighting proved to be the best sequence for soft tissue volume segmentation, allowing determination of the cause and degree of posttraumatic enophthalmos in reconstructed orbits.     

Deformation and fracture mechanisms in filled polymers

As fillers are traditionally designated those finely divided solids which are added to a polymer matrix in relativly large amounts to modify its properties and/or to reduce the price of the resulting compound. Generally a filler material is stiffer than the matrix and depending on their origin, shape and treatment fillers are reinforcing or not. In this presentation the authors will briefly review the characteristic mechanical effects on small strain behaviour, structure and time‐dependent properties of filled polymers stemming from the addition of more or less “spherical” fillers such as calcium carbonate, quartz flour, silica or glass spheres. The effect of such fillers on yield deformation, the nature of possible damage proceeding fracture and their effect on the toughness of particulate filled thermoplastics and thermosets will be discussed in more detail.