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  • 1
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Translational diffusion and internal motion have been observed by dynamic light scattering of optically labeled single chains of polystyrene (PS) in a semidilute solution of poly(methyl methacrylate) and benzene for the case in which the dimension Rg of the PS chain is comparable to the correlation length of the matrix solution. The molecular weight Mw dependence of the hydrodynamic radius Rh is expressed as Rh ∼ Mw0.91, while Rh ∼ Mw0.54 in pure benzene. The average linewidth Γ for internal motions (KRg 〉 1) appears to depend on the magnitude K of the scattering vector approximately as Γ ∝ K4 at higher KRg ( 〉 1), in contrast with the fact that Γ ∝ K3 approximately for KRg 〉 1 in pure benzene. The scaling law for the K dependence of Γ does not hold in low-molecular-weight PS owing to the K dependence of Γ/K2 for KRg 〈 1.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single-crystal mats of ultrahigh-molecular-weight polyethylene can be drawn uniformly to high draw ratios, more than 20χ at the highest, after the necking process is completed. The dynamic mechanical modulus of the drawn mats increases markedly during the uniform drawing stage. The structural changes induced by the uniform drawing at 100°C have been followed by wide-angle and small-angle x-ray scattering, infrared absorption, differential scanning calorimetry, and birefringence. The crystallinity is estimated from the x-ray amorphous scattering intensity, the IR absorbance of gauche bands, the heat of fusion from DSC, and the density. The estimated crystallinities of the drawn mats are all very high and increase slightly and monotonically with increased drawing after necking, though the values of the crystallinity depend on the method of estimation. IR gauche bands and the SAXS peak due to the long period disappear at a draw ratio of about 80χ. All the results suggest that the uniform drawing after necking destroys the two-phase structure made up of alternately stacked crystalline and amorphous regions and then reorganizes it into a single-phase crystalline structure.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fracture mechanics was used to investigate the environmental stress cracking of low-density polyethylene with 4.0 melt flow index. Annealed samples were prepared; a single edge notch was made and then the samples were fractured under constant load in four different liquid alcohols. The relation between the stress intensity factor K and the crack speed a· has been investigated. The log a· vs. logK curves are influenced not only by temperature but also by the alcohol used as the environment. This influence has been studied in detail. The conclusions are as follows: the crack speed at high K is determined by the diffusion mechanism, and this mechanism cannot be explained in terms of hydrodynamics but can be explained in terms of thermally activated molecular motion. On the other hand, the crack speed at low K is strongly related to the plasticization and the stress relaxation of the crack tip material.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The precise pressure dependence of apparent diffusion and permeation coefficients was measured by using a microcomputer system for collecting and treating permeation data for CO2 in glassy poly(ethylene terephthalate) below 1 atm between 15 and 40°C. The partial immobilization model was used to determine the dual-mode sorption and mobility parameters. The curves calculated with these parameters were in excellent agreement with experimental data. These parameters were also compared with sorption parameters obtained from measurements at 30°C. There was a small difference between the values of the parameters obtained from these permeation data and those from sorption data which we had previously obtained. Relations between this difference and the method of determination of the parameters are discussed.
    Additional Material: 7 Ill.
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  • 5
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Biaxial stress relaxation data acquired for a carbon-black-filled elastomer are analyzed. Consistent with previously published simple-tension and pure-shear results for this elastomer, the biaxial relaxation behavior is also found to be a separable function of time and strain effects. A departure from separability is observed at the larger strain; this might be a manifestation of strain-induced crystallization. An analysis of the biaxial results together with the earlier reported simple-tension and pure-shear data reveals that the deformational dependence of this elastomer obeys the Valanis - Landel hypothesis up to moderate deformations. The Ogden strain energy function is found to be an excellent analytical representation of all of the multiaxial data. Large relative errors found at small tensile strains between the data and the Ogden fit are attributed to carbon black structural effects.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheology of hydroxypropylcellulose (HPC) - acetic acid solutions was investigated by using a cone-and-plate rheometer and a capillary rheometer, for polymer concentrations ranging from 10 to 80%. Isotropic solutions exhibit a Newtonian plateau followed at higher shear rates by a pseudoplastic zone. The apparent viscosity varies as C5.2 if concentration C is less than 27% and as C13 for 27% 〈 C 〈 30%. A biphasic interval (isotropic and cholesteric phases) exists between 30 and 35%. A maximum in viscosity is observed at C = 30%, the height of the viscosity peak being a decreasing function of shear rate. Anisotropic solutions are strongly viscoelastic. Both isotropic and anisotropic solutions give results (apparent viscosity, first normal-stress difference, relaxation time, etc.) which are not in good agreement with Doi's theory. This is understandable since the HPC chain cannot be modeled by a rigid rod. Upon heating, anisotropic HPC - acetic acid solutions undergo an anisotropic to isotropic phase transition which is easily detected by a maximum in the temperature dependence of the first normal-stress difference and of the apparent viscosity.
    Additional Material: 13 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 8
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous investigations have given evidence of the existence of specific chemical interactions between poly(bisphenol-A carbonate) (PC) and a number of linear aliphatic polyesters, with the consequent formation of compatible polymer alloys. Here we address the particular kind of specific interaction that takes place in these systems by performing a quantum-mechanical study of the apparently most reasonable types of molecular interactions occurring in model compounds of the above polymers. Complete neglect of diffential overlap, (CNDO), in its CNDMEX version, and perturbative configuration using localized orbitals (PCILO) were the calculation schemes used on diphenyl carbonate (DPC) and dimethyl succinate (DMS), selected as models. It was found that, on a one-to-one basis, the DPC-DMS system is energetically more stable than the individual separate molecules; on examination of the possible interaction sites for the two chemical species, the interaction between the ester group oxygen in one DMS molecule with one of the phenyl rings in DPC appears to be the most favorable type of molecular interrelation, even though hydrogen bond formation is also possible between the oxygen atoms in DPC and the methylene hydrogens in DMS. (The former interaction decreases the total energy of the system by 0.12 kcal/mol, more than the latter.)
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  • 9
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the complex permittivity were used to study miscibility and phase behavior in blends of poly(vinyl chloride) (PVC) with two random ethylene - vinyl acetate (EVA) copolymers containing 45 and 70 wt % of vinyl acetate. The dielectric β relaxation of the pure polymers and blends was followed as a function of temperature and frequency for different blend compositions and thermal treatments. Blends of EVA 70/PVC were found to be miscible for compositions of about 25% EVA 70 and higher. Blends of lower EVA 70 content showed evidence of two-phase behavior. EVA 45/PVC blends were found to be miscible only at the composition extremes; at intermediate compositions these blends were two-phase, partially miscible. Both blend systems showed lower critical solution temperature behavior. Phase separation studies revealed that in the EVA 45/PVC blends, PVC was capable of diffusing into the higher Tg phase at temperatures below the Tg of the upper phase. In the blends, ion transport losses were significant above the loss peak temperatures, and in the two-phase systems, often obscured the upper temperature loss process. It was shown possible, however, to correct the loss curves for this transport contribution.
    Additional Material: 13 Ill.
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  • 10
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase separation temperatures of the ternary system polystyrene (PS) (Mw = 1.67 × 104)/poly(α-methyl styrene) (PαMS) (Mw = 9.0 × 104)/cyclopentane with a blend ratio PS/PαMS = 55/45 have been determined over the polymer concentration range 0.02 ≤ ψPS + PαMS ≤ 0.52, where ψ PS + PαMS is the segment fraction of polymer in ternary system. Phase separation temperatures for the upper critical separation in the ternary system decrease with increasing ψ PS + PαMS over the range 0.1 ≤ ψ PS + PαMS ≤ 0.52. The vapor - liquid equilibrium in this system with a blend ratio PS/PαMS=50/50 has been determined over the concentration range 0.925 ≤ ψPS + PαMS 〈 0.995 and the temperature range 60-100°C by the piezoelectric vapor sorption method. The polymer - polymer interaction parameters χ′12 determined are positive except at 100°C and increase with increasing ψ PS + PαMS. Values of χ′12 extrapolated to zero solvent concentration are positive (0.0-1.3) over the temperature range measured. Phase separation behavior is discussed in terms of phase separation temperature in a ternary system and the polymer-polymer interaction parameter.
    Additional Material: 6 Ill.
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