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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansion of a butadiene-styrene copolymer filled with carbon blacks differing tenfold in mean particle size (HAF and MT) was investigated. The glass transition was unaffected by MT and was raised only 0.2°C for every 10 parts per hundred by weight of polymer of HAF black added. The coefficient of expansion of the polymer component of the composite in the rubbery region was substantially unaffected by either carbon black, but decreased markedly with increasing black loading in the glassy state. These results suggest that free volume is not altered appreciably by the presence of the filler in the rubbery state, but expands with decreasing temperature below Tg. The latter effect is explained by dilatation due to stresses set up around filler particles, arising from differences in the expansion coefficients of filler and polymer, which are not relieved in the glassy state. The near invariability of Tg and of the rubbery fected by adsorption of polymer segments on the carbon black surface. A conservative rough estimate indicates that restriction of segmental motion is confined to a 30 Å layer around the particles in which Tg is elevated by only 10°C.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enchanced low-shear melt viscosity of branched polybutadienes is shown to be sensitive to dilution with low molecular compounds. The viscosity of branched polymers falls more rapidly with dilution than that of linear polymers, i.e., branched polymers show increased response to plasticization. At least one instance is demonstrated in which the viscosity ratio ηbr/ηlin reverses from a value greater than unity to less than one in passing from dry polymer to rubber extended with relatively large quantities of oil.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Steady flow and dynamic viscosities were determined for symmetrical linear and starbranched block copolymers of butadiene and styrene above their upper (polystyrene) glass transition. Block structures examined were B-S-B, (B-S-)3, S-B-S, (S-B-)3 and (S-B-)4. At constant molecular weight and total styrene content viscosities were greater for polymers terminating in styrene blocks, irrespective of branching. Branching decreased the viscosity of either polybutadiene-terminated or polystyrene-terminated block polymers, compared at equal Mw. However, comparisons at equal block lengths showed that the length of the terminal blocks, not the total molecular weight, governs the viscoelastic behavior of these polymers to a surprisingly good approximation. This unusual result is rationalized in terms of the two-phase domain structure of these polymers, which persists to a significant degree in the melt. Below the glass transition of the polystyrene blocks the effects of branching were masked by differences in the morphology of the domain structure unrelated to branching.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method described for the determination of molecular weight and long-chain branching distributions of polymers requires no prior knowledge of the functional relation between branching frequency and molecular weight. It is based on preparative fractionation and viscometric and gel-permeation chromatographic measurements on both fractions and whole polymer. The technique is applied to several polybutadienes and butadiene-styrene copolymers differing widely in method of synthesis and pattern of long-chain branching.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic properties of S - B - S block copolymers were measured in the tensile and shear deformation modes. Between the glass transitions of the polybutadiene and polystyrene domains the ratio of storage moduli E'/G' in tension and in shear for the same polymer varied from 3 to more than 30, depending on sample preparation. For films cast from good solvents this ratio was near 3; large ratios resulted from deposition from poor polybutadiene solvents or from compression molding. Above the polystyrene glass transition, E'/G' approached 3 for all samples. The effect is ascribed to various degrees of polystyrene domain connectivity. Electron micrographs confirm this interpretation. For morphologies of high polystyrene domain connectivity, the loss tangent in tension is heavily weighted by mechanical losses in the polystyrene phase; the loss tangent in shear is affected only moderately by differences in domain morphology.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic properties of block copolymers of styrene with butadiene or isoprene are consistent with the growth of a diffuse interphase or interlayer as block lengths decrease. Under the conditions of the present study the interlayer does not lead to a secondary loss maximum between the two domain glass transitions. The pattern of shifts of the loss maxima characteristic of the domain Tg's suggests strongly that the interlayer composition profile must be asymmetric with an average volume composition rich in styrene. Typical block polymer viscoelastic behavior is observed even beyond the point at which the interlayer attains 100% of the polymer volume. Such block polymers no longer contain compositionally pure phases, but are visualized as retaining a residual domain structure in which composition fluctuates between ever narrowing limits as blocks become shorter, approaching homogeneity and the mechanical behavior of random copolymers.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,4-Diphenyl-1,3-butadiene reacts readily with sec-butyllithium in toluene to form adducts. Although this 1,4-substituted conjugated diene did not homopolymerize or copolymerize with styrene, with butadiene it formed copolymers having compositions varying from one end of the chain to the other. The monomer reactivity ratios found were r1 = 8.2, r2 = 0 in toluene and r1 = 2.1, r2 = 0 in toluene-tetrahydrofuran (0.2%) solution. The intramolecular composition distribution of these polymers varied from an initial butadiene-rich composition, dependent on the ratio of monomers charged, to the equimolar composition of the alternating copolymer. In spite of this compositional heterogeneity, the crosslinked polymers exhibited a single glass transition characteristic of the mean composition. A secondary, high-temperature dispersion observed in the dynamic viscoelastic properties of some of the products is shown to be attributable to network topological effects.
    Additional Material: 9 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the strain-induced crystallization of a crosslinked 89% trans-polypentenamer was studied as a function of temperature and strain by using a combined birefringence - stress relaxation technique. The crystallization rate was found to be extremely sensitive to both variables and was, within experimental error, a function of the degree of undercooling alone, the increase in crystallization rate with strain being a direct consequence of the melting point elevation. From the isothermal, isometric crystallization rates, the development of crystallinity in constant-rate-of-strain experiments was calculated and related to characteristics of the stress--strain curve and of the temperature-strain rate dependence of tensile strength. These calculations allow one to estimate under what conditions sufficient crystallinity may be expected for the attainment of high strength in absence of reinforcing fillers. Crystallinities measured in this work were of the order of 10% or less. A limited x-ray diffraction study confirmed the low order of crystallinity indicated by the stress-birefringence measurements. The relatively high precision of the latter makes this technique attractive for the estimation of small straininduced crystallinities in rubbers.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Second virial coefficients have been measured in tetrahydrofuran for a series of anionically polymerized narrow distribution homopolymers and copolymers of butadiene and styrene. The results fit the general empirical equation A2 = M-1/4(0.0216wB + 0.00995wS + CwBwS), where M is the polymer molecular weight, wB and ws are the weight fractions of butadiene and styrene, and C is a constant which is zero for block polymers and equal to 7.9 × 10 - 3 for random copolymers. The equation is independent of the degree of 1,2 addition of butadiene and fits data on both linear and tetrachain star-branched polymers within experimental error.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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