1994 рік

Deformation of crack-tip crazes was measured on poly(vinyl chloride) by the optical interference method when the fatigue crack grew discontinuously. The changes in the craze displacements and stresses during a crack growth retarded period were then analysed. With load repetition, crazes increase their size and deform rubber-elastically. Employing the inverse Langevin approximation, a model was proposed that attributes the increase of rubber-elastic extension to the increase of random links between tangled junctions of molecular chains in craze fibrils through disentanglement. The number of links was found to increase almost linearly with repetition. The model explains the change of craze stress-extension relation and also the difference of fracture-surface roughness

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of 4-methoxyphenylacetica cid, and 2-hydroxyethylmethacrylateH, , prepared by free-radical polymerization in solution at low conversion, were analysed by 1H (300MHz) and 13C (75.5MHz) nuclear magnetic resonance spectroscopy, in terms of sequence distribution and stereochemistry of monomeric units along the copolymer chains. The concentration of M- and H-centred sequences was determined experimentally from the analysis of the ~-CH 3 resonance signals of M and H units, which gave a relatively complex pattern assigned to M and H centred triads with specific composition and stereochemical configuration. The carbonyl carbon group of M and H gave resonance signals with different chemical shift sensitive to sequences of tactic pentads, independently of the chemical composition. The experimental results were in fairly good agreement with those calculated statistically, taking into consideration the terminal copolymerization model and Bernoullian distribution of stereoregularity, with the statistical parameters Pij and Pu determined from the reactivity ratios rM= 1.49 and rn=0.61 and the stereochemical parameters a~M=0.27, ann=0.21 and o-* : O'MH = O'HM : 0.30

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The kinetics of chain degradation of purified granules of poly(/3-hydroxybutyrate) in 3.0 N HCI at the boil were followed using gel permeation chromatography to detect changes in molecular weight of the residue. The results showed that degradation corresponded to a model of random scission of the molecules of both the crystalline shell and the non-crystalline core indiscriminately. Differential scanning calorimetry and wide-angle X-ray diffraction results demonstrated that the molecules recrystallize due to chain scission and annealing at the temperature at which degradation is performed (104.5°C). Transmission electron microscopy of enzyme-isolated, spray-dried granules revealed a retention of the surface shell throughout the reaction with conversion of the core to a porous lamellar texture.

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Phenol-formaldehyde (PF) resin is a widely used adhesive in the manufacture of wood composites. However, curing behaviour of the resin under various environmental conditions is not well known. A differential scanning calorimeter was employed to characterize the degree of resin cure in this study. Resin-impregnated glass cloth samples with varied moisture contents (0, 31, 71%) were exposed to an environment of controlled temperature (105, 115, 125, 140°C) and relative humidity (41, 75, 90%) for a series of time periods (0-20 min). The samples were next conditioned to different levels of relative humidity (0, 64, 89%) before being sealed in d.s.c, capsules. The degree of cure of these partially cured samples was then determined by d.s.c, by measuring the residual heat of cure. The results show that the degree of resin cure increased with increasing precure temperature and time. The rate of cure increased for dry samples as precure humidity increased. However, the rate of cure decreased with an increase in the initial moisture content of samples when precured at 90% relative humidity. The effect of moisture put into a sample immediately before analysis by d.s.c, on the subsequent calculation of resin precure became less significant with increasing precure temperature and degree of resin cure

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A new model is proposed for rapid evaluation of the degree of long-chain branching in polymers, which correlates the intrinsic viscosity and the molecular weight. Intrinsic viscosity is expressed as a simple inverse tangent function of molecular weight. The model is based on the observation of theological behaviour of polymer melts and solutions. It can describe the intrinsic viscosity behaviour over a wider range than the Mark-Houwink equation. This model does not use trial and error procedure to decide the threshold molecular weight where the intrinsic viscosity starts to deviate from the Mark-Houwink relation. Calculation by the proposed model of the long-chain branching frequency of low density polyethylene shows good agreement with experimental results in the literature.

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A new method of measuring the efficiencies of free radical grafting reactions is presented. This technique utilizes the compositional analysis capability of dual-detector (ultraviolet and refractive index) gel permeation chromatography (g.p.c.) in which the mixture of polymers resulting from the graft copolymerization reaction is also subjected to separation by molecular size. Samples of the reaction mass drawn from a reactor are diluted with g.p.c, eluent and injected directly into the chromatograph without any other preparative step. Grafting efficiency, graft ratio, molecular weight distributions and the frequency of graft chains along the backbone polymer are simultaneously determined. Low molecular weight diluents (residual monomer, solvent, initiator, etc.) are readily separated from the polymer within the chromatograph, allowing for the determination of the fractional conversion of graft monomer (to grafted and ungrafted polymer) from the same analysis. This simple technique overcomes the need to separate or purify the polymer mixture prior to analysis, as required for most other methods. Experimental results are presented for the grafting of styrene onto cis-polybutadiene. Gelled samples cannot be analysed by this new technique

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The phase structure composed of the crystalline and non-crystalline phases, in particular the structure of the non-crystalline phase and hydrogen bonding, has been examined for poly(vinyl alcohol) (PVA) single crystals with different molecular weights by cross-polarization/magic angle spinning 13C n.m.r., differential scanning calorimetry and X-ray measurements. Although the molecular weight is vigorously decreased for the single crystals conventionally prepared from triethylene glycol solution, no reduction in molecular weight occurs when they are crystallized in a triethylene glycol/glycerol mixed solvent after dissolution at relatively low temperatures. According to the method previously reported, the triplets of the CH resonance lines of the crystalline and non-crystalline components have been analysed to obtain information about the intramolecular and intermolecular hydrogen bonds. It is found that the probability of formation of intramolecular hydrogen bonds in the meso sequence greatly differs between the crystalline and noncrystalline components, slightly or insignificantly depending on the molecular weight and the crystallization condition. It is finally concluded that PVA single crystals are composed of a crystalline phase with a thickness of about 8.0nm and a non-crystalline overlayer with a thickness of about 2.0nm. Moreover, the non-crystalline overlayer should consist of short loops with rather restricted molecular mobility compared to the mobility of the amorphous component.

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Styrene (ST)/butyl acrylate (BA) copolymers with average molecular weights as low as M,= 1500 and ~, = 3000, i.e. co-oligomers, were synthesized thermally at 230-280°C in a continuous stirred tank reactor without any added chain transfer agent. The products were characterized by size exclusion chromatography in conjunction with multiwavelength u.v., as well as by i.r., tH n.m.r, and differential scanning calorimetry. The molecular weights of the products decreased with increasing BA content in the monomer feed. The relationship between the residual monomer composition and the product composition can be modelled satisfactorily using a mathematical model based on the instantaneous copolymerization equation and Arrhenius relationships for the reactivity ratios. The devolatilized products varied in form from elastic semisolids through glue-like liquids to viscous liquids

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We investigated the spherulite growth rate G in 60/40 isotactic polystyrene (i-PS)/atactic polystyrene (a-PS) mixtures under a polarized microscope with a TV video recording system. When the molecular weight M A of a-PS was higher than 1.91 x 104, linear growth was observed, i.e. G was constant throughout the crystallization, and the chain diffusivity D T decreased monotonously with increasing M A. In contrast, when M A was less than 5.2 x 10 3, the growth was non-linear, i.e. G decreased with time, and D T increased with increasing M A (DTOCM~/2). Both M A dependences on D T were successfully interpreted using a modified Hoffman-Lauritzen theory involving the exclusion effect of a-PS. On the basis of this modified Hoffman- Lauritzen theory, the spherulite growth mode, i.e. linear or non-linear, was also interpreted in terms of a new kinetic parameter 2 = D~JD,, D* and D s being the tracer diffusion coefficient of a-PS and the self-diffusion coefficient of i-PS, respectively.

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