Nanoscale highly filled epoxy nanocomposite

A new technique has been developed to prepare a highly filled epoxy-montmorillonite (MMT) nanocomposite using an organically modified MMT. Composites with clay content up to 70 wt.% exhibit unusual transparency, which is related to the spatial distribution of the mineral nanodomains. Dispersion of the layered silicate within the crosslinked epoxy matrix was verified using X-ray diffraction pattern, revealing layer spacings of 30 and 70 Å. Examination of these materials by scanning electron microscopy and transmission electron microscopy showed that intercalates have wholly layered morphology at all scales, oriented parallel to the surface of the specimen and have good wetting to the silicate surface by the epoxy matrix. Silicate lamellae intercalated with epoxy resin assembled into a cluster of about 50-120 nm thickness. These clusters assembled into superclusters with an average thickness of 300 nm. Studies by the Vickers hardness test of an epoxy-MMT nanocomposite containing 60 wt.% MMT indicated that the diamond pyramid hardness was 10-29 kg/mm².     

Structural hierarchies and interactions in the tendon composite

Tendon functions by transmitting tensile loads from muscle to bone. Morphologically, it can be described as a macromolecular multicomposite material, basically consisting of collagen fibrils held together by a soft, hydrated matrix material. Recently, tendon has been deformed beyond the "in vivo" elastic limit and by cyclical loading systematically damaged. Using high-resolution electron microscopy, decomposition of the collagen fibril into subfibrils (15 nm diameter) and microfibrils (3.5 nm diameter) has been noted. The interfacial adhesion between such units is strongly dependent on age, and is probably related with crosslinking phenomena observed by biochemical methods. In addition, tendon collagen contains a considerable amount of water throughout the entire structure which strongly affects its overall mechanical behavior. The various bound states of water have been identified using primarily dynamic mechanical spectroscopy coupled with more conventional methods of structural characterization.Published in Mekhanika Polimerov, No. 4, pp. 693–701, July–August, 1976.     

Failure Processes in Fiber-Reinforced Liquid-Crystalline Polyester Composites

A hierarchical structural model for liquid-crystalline polyester reinforced with short glass fibers has been determined by using injection-molded bars. The gradient structure showed similar orientations between the glass fibers and the molecular orientation of the matrix. In the fiber-reinforced composites, the core failed prior to the skin by matrix cracking and transverse fiber pull-out as evidenced by the initial growth of parabolic cracks in the core. In the 30 wt% composite this was followed by complex cooperative phenomena involving fiber breakage, debonding, pull-out, and matrix deformation in the skin. The 50 wt% composite failed prematurely due to inadequate fiber/matrix interactions in the skin structure. Acoustic emission coupled with microscopy provided mechanistic insight throughout this work into the amount and intensity of specific failure mechanisms.     

Confined crystallization of PVDF and a PVDF‐TFE copolymer in nanolayered films

Layer‐multiplying coextrusion was used in conjunction with isothermal recrystallization to study the confined crystallization of polyvinylidene fluoride (PVDF) and polyvinylidene fluoride‐tetrafluoroethylene (PVDF‐TFE) using polycarbonate (PC) and polysulfone (PSF) as confining materials. Three layered systems were produced (PC/PVDF, PSF/PVDF, and PC/PVDF‐TFE) with layer thicknesses ranging from 525 to 28 nm. The crystal morphology was affected by both layer thickness and recrystallization temperature. Specifically, increased recrystallization temperature and decreased layer thickness facilitated the formation of high aspect ratio in‐plane crystals in both PVDF based polymers. On the other side of the spectrum, thicker layers and lower recrystallization temperatures produced on‐edge PVDF crystals and isotropic PVDF‐TFE crystals. The morphology was correlated with oxygen permeability, which decreased by almost two orders of magnitude compared with the bulk. A variety of crystal structures were obtained and explained with nucleation and diffusion theory. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Oxygen‐barrier properties of copolymers based on ethylene terephthalate

The oxygen‐barrier properties of amorphous polyethylene terephthalate‐based copolymers with various acid comonomers were examined. The incorporation of increasing amounts of isophthalate, phthalate, or naphthalate gradually reduced the permeability P toward the low values obtained for the corresponding homopolymers. The permeability of poly(ethylene 3,4′‐bibenzoate) homopolymer was only slightly lower than that of polyethylene terephthalate, and the copolymers correspondingly exhibited a very gradual decrease in P as the amount of 3,4′‐bibenzoate (3,4′BB) increased. In contrast, copolymerization with the linear isomer, 4,4′BB, produced a substantial increase in P. Generally, comonomer affected the solubility S less than the diffusivity D, and therefore changes in P reflected primarily changes in D for the polymers studied. The diffusivity and solubility depended on the copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility S correlated with the amount of free volume as determined by the glass‐transition temperature. Correlation of the diffusivity D with the magnitude of the subambient γ relaxation identified dynamic free volume with thermally activated conformational changes and segmental motions. Correspondence in the activation energy confirmed the relationship. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1889–1899, 2001     

PH-Bestimmungsmethoden

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Oxygen‐barrier properties of cold‐crystallized and melt‐crystallized poly(ethylene terephthalate‐co‐4,4′‐bibenzoate)

This study examined the oxygen‐transport properties of poly(ethylene terephthalate‐co‐bibenzoate) (PETBB55) crystallized from the melt (melt crystallization) or quenched to glass and subsequently isothermally crystallized by heating above the glass‐transition temperature (cold crystallization). The gauche–trans conformation of the glycol linkage was determined by infrared analysis, and the crystalline morphology was examined by atomic force microscopy. Oxygen solubility decreased linearly with volume fraction crystallinity. For melt‐crystallized PETBB55, extrapolation to zero solubility corresponded to an impermeable crystal with 100% trans glycol conformations, a density of 1.396 g cm^?3, and a heat of melting of 83 J g^?1. From the melt, PETBB55 crystallized as space‐filling spherulites with loosely organized lamellae and pronounced secondary crystallization. The morphological observations provided a structural model for permeability consisting of impermeable platelets randomly dispersed in a permeable matrix. In contrast, cold‐crystallized PETBB55 retained the granular texture of the quenched polymer despite the high level of crystallinity, as measured by the density and heat of melting. Oxygen solubility decreased linearly with volume fraction crystallinity, but zero solubility corresponded to an impermeable defective crystal with a trans fraction of 0.83 and a density of 1.381 g cm^?3. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2489–2503, 2002