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  • Physics  (10,668)
  • Wiley-Blackwell  (10,640)
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  • 101
    Electronic Resource
    Electronic Resource
    Conformational energy contribution to the heat of solution in polymer-solvent systems. Part II. Experimental results (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 855-866 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heats of solution (ΔHexp) in solvents of increasing thermodynamic power have been measured for four polymers: polystyrene (PS), poly(vinyl acetate) (PVAc), polyisobutylene (PIB) and polydimethylsiloxane (PDMS). After subtraction from ΔHexp of an interaction term (calculated by the Hildebrand treatment based on solubility parameters) and the excess volume term, the quantity remaining is interpreted as the conformational energy contribution (ΔUconf) to the heat of solution. ΔUconf appears to correlate well with some basic conformational properties of the chain, such as the sign of the temperature coefficient of unperturbed dimensions derived from solution properties, and shows a monotonic behavior with α, the expansion coefficient of the polymer coil in the final solution. Numerical values of ΔUconf, at least for those cases in which polymer solubility parameters are known with some certainty, are much larger than those evaluated from rubber elasticity experiments (through the experimentally accessible value of the energy component of the force of retraction im simple elongation).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160070510
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  • 102
    Electronic Resource
    Electronic Resource
    Swelling of crosslinked poly-4-vinylpyridine (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1101-1109 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinylpyridine of molecular weight 0.77 × 106 was crosslinked by 2.5, 5, and 10% BrCH2C6H4CO(CH2)8COC6H4CH2Br and by 10% ClCH2C6H4CH2Cl; quaternization of the gel was completed with n-butyl bromide. Swelling ratios in aqueous solutions of lithium, sodium, and 4-isopropyl-N-n-butylpyridinium bromide and in methanolic lithium bromide were determined. Selectivity increased in the sequence Li+ 〈Na+ 〈PrN+-C5H5. The Flory parameter χ1, which measures interaction between solvent and polymer, decreased from 1.5 kT to nearly zero with increasing density of crosslinks in the aqueous solutions, and from 3 kT to 0.5 kT in the methanol solutions. The inverse proportionality of q2/3 (q = swelling ratio) to the crosslinking density was approximately verified for swelling of the resins in water, methanol, and dimethylformamide.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160070610
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  • 103
    Electronic Resource
    Electronic Resource
    Spin lattice relaxation in linear polyethylene (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proton spin-lattice relaxation times (T1) of linear polyethylenes (PE) of varying morphology were measured as a function of temperature. The T1 of oriented bulkcrystallized and solution-crystallized material was isotropic, in disagreement with calculations based on a sample dipole pair model. Motion in the non-crystalline regions of the samples is shown to be responsible for the T1 minimum occurring around -20°C. The dependence of T1 at the minimum on the long period reinforces the model of an amorphous fraction composed of disordered lamellar surface layers. The temperature of the T1 minimum and the dependence of T1 on the long period imply that the mobility of these amorphous regions is reduced in cold-drawn and solution-crystallized samples. This mobility irreversibly increases with annealing. In highly relaxed samples the motion of a small portion of the disordered regions is almost liquidlike, as indicated by the presence of a second shorter T1.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160070703
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  • 104
    Electronic Resource
    Electronic Resource
    Structural and steric isomerism of polypropylenesThis work was presented in part at the 16th Polymer Symposium, Fukuoka, Japan, October 1967. (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 963-981 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl3-C2H5Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A2 vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm-1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH2 and CH(CH3) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm-1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160070601
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  • 105
    Electronic Resource
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    Relation between melting behavior and physical structure in polymers (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160070606
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  • 106
    Electronic Resource
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    Aromatic poly(amic acids): Fundamental structural studiesPaper presented at the 149th National Meeting of the American Chemical Society. Detroit, Michigan, April 1965.1 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 653-662 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aromatic poly(amic acids) derived from pyromellitic dianhydride and 4,4′,-diaminodiphenyl ether were characterized by dilute solution techniques. Number-average molecular weights M̄n of 13 samples ranged from 13,000 to 55,000 (DP 31-131). Weight-average molecular weights M̄w of 21 samples ranged from 9,900 to 266,000. The ratio M̄w/M̄n was between 2.2 and 4.8. Heterogeneous polymerization yielded higher molecular weight polymer than homogeneous polymerization. The molecular weight could be varied systematically by control of stoichiometric imbalance. Use of very pure monomers and solvent gave polymers of relatively high number-average molecular weight (∼50, 000) and the most probable molecular weight distribution M̄w/M̄n = 2. Impure monomers and/or solvent resulted in lower number-average molecular weight (M̄n ≅ 20,000-30,000) and wider distributions (M̄w/M̄n = 3-5). The Mark-Houwink relation obtained was [η] = 1.85 × 10-4M̄w0.80 The exponent is characteristic of moderately extended solvated coils. The unperturbed chain dimensions (r02/M)1/2 were 0.848 A., and the steric factor σ was 1.24 which is close to the limiting value of unity for an equivalent chain with free internal rotations. The sedimentation constant-molecular weight relation was S0 = 2.70 × 10-2M̄w0.39. This exponent is consistent with the Mark-Houwink exponent.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050402
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  • 107
    Electronic Resource
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    Elastic properties of crosslinked poly(vinyl alcohol) gels: Network topology (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 663-670 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1967.160050403
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  • 108
    Electronic Resource
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    Solubility and diffusion of water in acetal polymers (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 671-684 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of water sorption at 25°C. has been determined for a number of polyacetal films differing in structure, density, and orientation induced by extrusion. The equilibrium water uptake was found to be a linear function of density only; no other effect of structure or orientation was detectable. The extrapolated density for zero sorption was 1.51 g./cc., not far from the theoretical crystalline density. The diffusivity of water in unoriented films rose with decreasing density; for linear copolymer, the trend was parallel to that of the area under the dynamic mechanical loss peak associated with long-range chain motions in the disordered regions (β-transition). Less pronounced effects of molecular weight and long chain branching on diffusivity were also noted. Films crystallized while an extruded melt was still oriented showed considerable increases in water diffusivity, but no significant changes in the apparent activation energies of permeation (about 6.6 kcal./mole) or diffusion (about 11.5 kcal./mole). On annealing these films, the diffusivity remained almost constant while the sorption coefficient and retraction on remelting decreased.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050404
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  • 109
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    Streaming birefringence. VII. Influence of the intermolecular hydrodynamic interaction on the viscosity and streaming birefringence of polymer solutionsPart VI, see Munk.1 (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 685-696 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cavity model used in the theory of dielectrics was applied to hydrodynamics to calculate the force exerted by a system of soft dumbbells on a reference dumbbell in a hydrodynamic field. The influence of this force on the viscosity and flow birefringence and its dependence on both the concentration and velocity gradient were calculated. The system of equations has a real solution only for values of β = M[η]η0γ/RT which are smaller than a critical value rapidly decreasing with increasing concentration. At zero concentration the results obtained agree with the theory of a single isolated dumbbell model. The calculated Huggins constant is k′ = 0.4. The extinction angle is connected with the relative viscosity very nearly as derived from experiments. However, the theory fails at higher concentrations and gradients yielding an increase in viscosity with the gradient and infinite zero-shear viscosity for the concentration c = 2.5/[η].
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050405
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  • 110
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    Tensile yield-stress behavior of poly(vinyl chloride) and polycarbonate in the glass transition region (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1745-1754 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield-stress behavior of two glassy polymers is studied through the glass transition region over a wide range of strain rates. For temperatures below the glass transition temperature, the yield stress behavior could be described as a non-Newtonian flow in agreement with Eyring's theory, if one excepts a narrow range relating to the slowest strain rates. For temperatures above Tg, the yield-stress behavior is still nonlinear but fits the relations based on the concept of free volume.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071010
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  • 111
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    Effect of immobilizing adsorption on the diffusion time lag (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1811-1818 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A “dual sorption” model has been proposed by Michaels, Vieth, et al. to explain extensive equilibrium sorption data for several gases in some glassy polymers. To explain data on sorption kinetics, it was further postulated that one of the sorption modes immobilizes the gas molecules. Stated mathematically, this model leads to a modified form of Fick's second law. Both normal and desorption time lags for diffusion have been computed here for this model of diffusion in glassy polymers. The computed time lags are shown to be dependent on the boundary concentrations used in permeation. Experimental measurement of these time lags would be a sensitive and critical test to ascertain the validity of this theory.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071015
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  • 112
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    Statistics of extreme values applied to the brittle fracture of poly(methyl methacrylate) containing polytetrafluoroethylene particles (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1863-1882 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl methacrylate) tensile bars were prepared containing nearly spherical polytetrafluoroethylene particles in concentrations from one to a thousand particles per gauge length of the bars. Particle diameters varied from 0.0035 to 0.018 in. Exhaustive tensile tests were performed at sufficiently high strain rate to assure brittle fracture and the results analyzed statistically by the theory of extreme values as proposed by Epstein. The results suggested that the polytetrafluoroethylene particles themselves did not act as flaws, but that they intensified the stress field on natural flaws which acted as the origin of fracture. Assuming a Laplace distribution as the underlying distribution of tensile strength (not to be confused with observed distribution of tensile strengths) gave predicted fracture statistics in good agreement with experiment.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1969.160071103
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  • 113
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    Molecular weight distribution in branched polymers (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1937-1954 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The distribution of molecular weights in realistic free-radical polymerizations with branching was analyzed theoretically. Series solutions were obtained for the fraction of molecules with r repeating units and the number of branch points contained in molecules with r repeating units. Branching by transfer processes was found to increase the proportion of both high and low molecular weight components in the system. The apportioning of branch points among r-mer molecules was shown to be somewhat narrower than a Poisson distribution. The major difference between the calculated distributions and previous model distributions for branched systems was the absence of discontinuities in the moments at all levels of branching.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071108
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  • 114
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    Glass transition of stretched natural rubber (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1983-1986 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071111
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  • 115
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    General dynamic theory of macromolecular networks. I. Definitions and classification (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2005-2018 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of the structural theory of macromolecular networks is formulated and discussed in general terms. The conditions required for a system to become a homogeneous macromolecular network are defined and discussed. Networks are divided according to the nature of their junctions into three classes: energetic (with chemical or quasi-chemical crosslinks), topological (with entangled chains), and contact (with frictional interactions). The main features of these three classes are discussed. A distribution density function ψ describing the configurations of macromolecules in network systems is introduced. The phase space of variables is 4(N + 1)-dimensional and includes the coordinates of (N + 1) vectors hi joining the adjacent network junctions and (N + 1) contour lengths li of the network chains. The system of simultaneous equations required for the determination of the function ψ includes the equation of continuity, kinematic equations for the deformation velocity of the individual junctions, the force balance equation needed for the determination of sliding rates li, kinetic equations for the processes of junction breakage and reformation, and the equilibrium distribution of network junctions defining the initial conditions for the distribution function ψ.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071203
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  • 116
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    Extended-chain crystals. III. Size distribution of polyethylene crystals grown under elevated pressure (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2061-2072 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extended-chain crystals of high molecular weight polymethylene, a polyethylene with a broad molecular weight distribution, and three fractions of polyethylene were grown from the melt under elevated pressure. Comparison of the crystal size distribution in the molecular chain direction (measured on fracture surfaces by electron microscopy) with the molecular weight distribution (measured by gel-permeation chromatography) gave the following results. Up to molecular weight 10,000 all samples showed eutectic separation into fully extended chain crystals of narrow molecular weight distribution. Above molecular weight 10,000 mixed crystals were formed. Under the chosen crystallization conditions larger chain extension was achieved with higher molecular weights. However, an increase in molecular weight by a factor of 1000 led only to a tenfold increase in chain extension. These facts are discussed in the light of a proposed mechanism of crystal growth.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1969.160071208
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  • 117
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    Birefringence and dichroism of rubbery copolymers (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2115-2138 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Kuhn-Grün theory for the birefringence and dichroism of rubbery polymers is extended to the case of copolymers consisting of two or more statistical segments of differing lengths. It is shown that the previous equations are applicable provided that the anisotropy of polarizabilities and absorptions are replaced with suitable averages in which the segment anisotropies are weighted by the squares of their segment lengths. This indicates that the stress-optical coefficient will not generally vary linearly with composition. The orientation measured from the dichroism of bands arising from different segments will be different.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1969.160071212
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  • 118
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    Surface and colloid science. Vols. 1 and 2. EGON MATIJEVIC, Ed., Wiley-Interscience, New York, 1969. Vol. 1, 298 + vii pp.; vol. 2, 260 + vii pp. (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2142-2143 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071216
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  • 119
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    Preparation of long-chain paraffins from nitric acid degradation products of polyethylene; some consequences for polymer crystal structure studies (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 19-34 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that dicarboxylic acids of uniform lengths, obtained by degrading chain-folded polyethylene single crystals, can be converted to paraffins via the intermediate diiodide by means of the procedure of Barton et al. Thus we are now in the position of obtaining uniform paraffins of chain lengths longer than hitherto available for the study of the crystallization of oligomeric chains. Measurements of melting points and heats of fusion revealed major differences between the paraffins and the corresponding parent dicarboxylic acids. It follows that such measurements on the unmodified products of the nitric acid degradation cannot be used directly for the assessment of the chain traverse length and the degree of crystallinity. It was found further, that the intermediate diiodide is a sufficiently close approximation to the paraffin for the purposes just quoted.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080102
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  • 120
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    Universal calibration in GPC: A study of polystyrene, poly-α-methylstyrene, and polypropylene (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 89-103 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical justification for using M[η], or a similar quantity, as a universal calibration parameter in GPC is reviewed. The equation based on this parameter is applied to transform the primary calibration curve, obtained by means of polystyrene samples, into calibration curves for poly-α-methylstyrene, polypropylene, and linear polyethylene. The Mark-Houwink equations for these polymers, as they are used in the transformation, are discussed. The resulting GPC calibration curves are compared with molecular weights and peak elution volumes of fractionated poly-α-methylstyrene and polypropylene. The same comparison is made with samples of polypropylene and polyethylene having very broad molecular weight distributions. The agreement lies within experimental error.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080108
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  • 121
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    Calibration of gel-permeation columns with unfractionated polymers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 148-152 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080112
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  • 122
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    Addition polymers: Formation and characterization. D. A. SMITH, ed., Plenum Press, New York, 1968. pp. 492. $22.00 (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 482-482 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080314
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    Precipitation chromatography theory (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 207-224 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A discussion is given of the behavior of a mathematical model chosen to approximate conditions during precipitation chromatographic fractionation of polymer (Baker Williams fractionation). With only one molecular weight species of polymer a complete solution of the mathematical model was obtained. With more than one species it was necessary to use a computer solution. Curves showing the movement of polymer containing one and two species of polymer are given for a variety of conditions of operation. It was found that the degree of fractionation of polymer approaches a limiting value with increasing length of column. Under some conditions the degree of fractionation may go through a maximum with length of column. The equilibrating distance (distance of travel of the liquid phase required to establish equilibrium of polymer between the liquid and the bed) was found to be very important in determining the fractionation.
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    Dynamic and steady-shear melt rheology of and ethylene-methacrylic acid copolymer and its salts (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 277-287 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies have been made on the dynamic and steady-shear melt rheology of an ethylene-methacrylic acid copolymer and two of its salts obtained by partial neutralization with sodium and with calcium bases. Measurements were made with a Weissenberg rheogoniometer over a broad range of shear rates and frequency in the temperature interval mainly from 100 to 160°C. The temperature coefficients of dynamic and steady shear viscosity are evaluated at both constant shear rate and constant stress. Likewise, complex dynamic viscosities and apparent high steady-flow viscosities and intercompared at equivalent frequencies and shear rates. The un-ionized acid copolymer shows good correlation between the frequency dependence of the complex viscosity and the shear rate dependence of the apparent viscosity. This is not true for either the sodium salt or the calcium salt. These results are consistent with the two-phase structural model for these materials, i.e., a matrix of hydrocarbon in which are embedded ionic domains.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080206
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    Effect of diluents on the melt viscosity of branched polybutadienes (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 305-310 
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    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.
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    Normal stress and shear stress in a viscoelastic liquid under oscillatory shear flow (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 371-381 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Normal stress and shear stress of concentrated polystyrene solutions in a chlorinated diphenyl were measured under steady flow and oscillatory shear flow in a Weissenberg rheogoniometer. The normal stress difference was observed to oscillate at double the frequency of the applied shear strain with amplitude proportional to the square of the applied amplitude, while the shear stress was found to oscillate at the same frequency with amplitude proportional to the applied amplitude. A theoretical relation between the displacement of the oscillatory normal stress difference from zero level and the dynamic modulus derived by Lodge and other investigators was confirmed experimentally, and the theoretical predictions of Coleman and Markovitz concerning the relation among steady-flow normal stress difference and dynamic modulus were also confirmed. However, the theoretical predictions of Lodge, of Spriggs, Huppler and Bird, and of Williams on the relation between the amplitude and phase of oscillatory normal stress and those of oscillatory shear stress did not agree with experimental results.
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    Network behavior of polyurethane elastomers (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 839-852 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present study is concerned with some network properties of polyurethane elastomers in which stability is acheived via physical crosslinkages such as microcrystallites or secondary bonding. The techniques of isothermal, thermo-, and photoelasticity have been used to gain better insight into the mechanisms which occur during the deformation of these materials. It was found that stable networks are obtained only after mechanical and thermal conditioning. The well-known stress lowering which is observed during the second deformation is manifested primarily in the entropy component of the retractive force. This implies that the stress lowering results from a reduction in the number of effective network chains and not from time-dependent effects or crystallinity changes. Depending upon the chemical structure of the material, both positive and negative energy components of the force have been found.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050504
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    Viscoelastic properties of polystyrene (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 875-889 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An extension of the results of a previous to higher molecular weights is made. The viscoelastic parameters ηt, Je, τm, and Em are found experimentally through stress relaxation tests. The predictions of the Rouse-Bueche (RB) theory and its modified Ferry, Landel, Williams (FLW) form concerning the molecular weight dependencies of these perameters are compared with the data. It is found that the RB and FLW predictions are not rigorously obeyed.
    Additional Material: 11 Ill.
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    Technical dictionary of high polymers. WLADIMIR DAWYDOFF and HORST HOWORKA, Pergamon Press, New York, 1969, 959 pp. $10.00 (1969)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2141-2142 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1969.160071215
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    Single crystals of high polymers by film formation (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 47-59 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method of preparing thin uniform films of high polymers has been examined for growing single crystals from solution. Single crystals of polyethylene, polypropylene, polybutene-1, polyacrylonitrile, and cellulose triacetate have been obtained by this method. Different stages of growth reveal different growth features that are also obtained from solutions of these polymers by changing temperature and concentration.
    Additional Material: 19 Ill.
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    Isomorphic interactions of ethylenic polymers and paraffin wax (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 81-87 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The high degree of flexibility of blends containing minor amounts of partly crystalline copolymers of ethylene and vinyl acetate in paraffin wax seems to be a manifestation of some type of interaction. Low-angle x-ray diffraction of such blends showed a new long spacing intermediate in length between the polymer long spacing and the c axis length of the wax unit cell. This new long spacing appears to be a consequence of isomorphism involving cocrystallization of polymeric ethylene sequences and wax molecules. A lesser type of isomorphic interaction, epitaxy, occurs in polyethylene-wax blends: wax overgrows crystals of already crystallized polyethylene in the same orientation without a change in its c axial dimension.
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    Thermoluminescence in hydrocarbon polymers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 143-147 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080111
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    Yield condition and propagation of Lüders' lines in tension-torsion experiments on poly(vinyl chloride) (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 893-901 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have derived from the Eyring theory of non-Newtonian flow a yield condition which is valid for an arbitrary state of stress. Experimental data obtained in simple axial compression tests show the influence of the hydrostatic stress on the yielding of poly(vinyl chloride). This fact confirms the proposed condition and disproves the von Mises criterion. Tension-torsion tests performed on thin tubes lead to results which fit our condition fairly well. The pattern of Lüders' lines appearing on the surface of thin tubes subjected to simple tension, simple shear, and tension-torsion are parallel to the direction where the value of the normal stress is equal to the hydrostatic stress.
    Additional Material: 8 Ill.
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    Fusion of homopolymers and ordered copolymers containing ethylene sebacate structural units (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 957-967 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.
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    Internal motion in organosilicon polymers. II. Dimethylpolysilazanes crosslinked through silicon (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 999-1010 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the internal motion in organosilicon polymers by wideline nuclear magnetic resonance has been extended to a pair of dimethylpolysilazanes crosslinked through trifunctional silicon. The data suggest that there is considerable internal motion in all silazanes at 77°K. Evidence is presented for the presence of C3 rotation of the methyl groups, as well as rotation or torsional oscillation of the Si(CH3)2 groups about the polymer backbone. Upon warming the NMR line is seen to narrow, and this is associated with the onset of additional motion, including chain translation and chain flexing or bending. Crosslinking through silicon increases the barrier to chain translation while decreasing the barrier to chain flexing or bending.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080614
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    Structure and properties of poly-2,5-distyrylpyrazine (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1027-1037 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-2,5-distyrylpyrazine (poly-DSP) was investigated by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and measurements of dynamic viscoelastic and electrical properties. From DTA and TGA studies it was confirmed that poly-DSP melts at 321°C and depolymerizes rapidly to the monomer at temperatures between 335°C and 345°C in helium. The polymer is affected by oxygen above 200°C. The E′ value from dynamic viscoelasticity measurements on amorphous film is 2 × 1011 dyne/cm2 at room temperature. It decrease abruptly in the temperature range 140-150°C; but the net decrease of E′ within this temperature range is relatively small. The electrical properties of amorphous poly-DSP are characterized by a small temperature dependence of the dielectric constant between room temperature and 100°C. The dielectric loss tangent was observed to be small, and the dc conductivity was extremely small. It is concluded that rotation of the phenyl branches in the polymer occurs above -30°C and the glass transition occurs at about 150°C. These properties are discussed in some detail in relation to the polymer structure.
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    Comonomer and stereosequence distributions in high polymers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1111-1126 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Comonomer and stereosequence distributions in linear high polymers are considered from the point of view of the general theory of stationary random sequences. Although the discussion is centered about binary polymerizations which may be regarded as stationary Markov processes of low order, attention is paid to distinguish results valid for any stationary random process including stationary non-Markov processes from those special to a particular Markov process. Alternative derivations of copolymer composition equations are given along with a corrected version of a previously suggested scheme of relating conditional probabilities of different orders. The nature and relative merits of the several measures proposed in the literature to characterize comonomer and stereosequence distributions are also discussed in some detail.
    Additional Material: 2 Tab.
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    Dielectric absorption in oriented poly(vinylidene fluoride)Paper presented in part at the 16th Annual Meeting, Society of Polymer Science of Japan, Tokyo, 1967. (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1177-1186 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(vinylidene fluoride) is affected by orientation and crystal modification. The loss peak caused by molecular motion of the molecules in crystalline regions appears at about 70°C (110 Hz) (α1 absorption) for the α form, and at about 110°C (110 Hz) (α2 absorption) for the β form. Orientation significantly affects the magnitude of the β absorption which appears at about -40°C. The very high value of the dielectric constant for stretched film is believed to be due to the orientation effect. The γ absorption, which is assumed to be local-mode absorption, is not so much affected by orientation. An additional loss peak has been found at around 0°C in dynamic mechanical measurements, but the molecular mechanism is unknown.
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    A dynamic approach to diffusion and permeation measurements (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 467-479 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic method for investigating the mechanism of permeation and diffusion through polymers has been explored. The permeation cell consists of two compartments separated by the membrane. The permeant (gas, vapor, or liquid) is introduced into one compartment; a carrier gas (helium) flows at constant rate through the other and sweeps the permeant which diffuses through the membrane to the thermal conductivity detector. Both compartments are at atmospheric pressure; thus no or little membrane support is required, and leakage problems are minimal. Moreover, the same membrane can be used over a wide temperature range and for diverse permeants. The detector signal is at any instant proportional to the permeation rate. A simple mathematical formalism for deriving the diffusion coefficient from the transient permeation rates has been developed. The measured diffusion and permeability coefficients of CO2, O2, and N2 through low-density polyethylene closely agree with literature values. Permeation of hexane and benzene through polyethylene follows a complex diffusion law, and the rate depends on the thermal history of the system. The dynamic method is particularly suited to the study of transitions in polymers. Changes in permeation rates, usually occurring at transition points, can easily be discovered by slow temperature scanning of the system.
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    Statistical mechanics of chain molecules. PAUL J. FLORY, Wiley (Interscience), New York, 1969, 432 pp. $17.50. (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 487-487 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080317
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    Multiple melting transitions in fractions of partially isotactic poly(propylene oxide) (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 519-528 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three transitions are detected dilatometrically when partially isotactic poly(propylene oxide) melts. One transition, the temperature of which is independent of the crystallization temperature over a wide range below 60°C, is ascribed to the melting of lamellar crystallites which are limited in thickness by the average isotactic sequence length alone. The other two transitions, the temperatures of which vary with the crystallization temperature, are ascribed to the melting of lamellar crystallites with thickness determined predominantly by three- and two-dimensional primary nucleation acts. The theory of Flory is adapted and applied quantitatively to the melting points of three crystalline fractions of poly(propylene oxide), obtained from a polymer produced via the zinc diethyl and water catalyst system. This method leads to a thermodynamic melting point of isotactic poly(propylene oxide) near 82°C.
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    Fracture surface of polystyrene: Mackerel pattern (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 583-594 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic markings of concentric bands are formed on the fracture surface of tensile specimens under certain loading conditions. The marking form in the fast crack growth region of the mirror area of fracture. Optical and electron optical microscope techniques have been used to study the morphology of the markings. It is shown that in this region the crack propagates along the interface between the craze, in which the crack nucleated, and the bulk material. The mackerel pattern is caused by the crack jumping from one craze-matrix interface to the other.
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    Tensile properties and equilibrium swelling of plasticized amorphous polyurethane rubbers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 605-624 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Incorporation of plasticizers or other inert, liquid diluents causes a profound weakening of rubbers. The modulus of elasticity and tensile strength decrease approximately with the square of the gel fraction v0 of rubber which was present at the time of formation of the three-dimensional network. Equlibrium swelling of plasticized rubbers is well represented by v2m = kv0, where v2m is the volume fraction of rubber network in the swollen state, at equlibrium, and k a constant equal to v2m for the unplasticized rubber. This swelling law is independent of the way in which v0 is obtained; inert liquid diluents, comprising molecularly dispersed compounds, as well as suspensions of insoluble liquids, gases, and chemically inert, solid fillers yield the same relation. Further, it is independent of the chemical nature of solvent and rubber. It appears that also the mechanical properties of foams, liquid-filled foams, and plasticized elastomers containing the same volume fraction of network rubber are very similar.
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    Multiple melting in isotactic polystyrene (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 649-652 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080415
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    Viscoelastic and relaxation properties of a polystyrene melt in axial extension (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 657-678 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On axial extension of polymer melts at constant deformation rates, the development of high-elastic deformation is of predominant importance during the initial period. High-elastic deformation is accompanied by a rise in viscosity and in the modulus of high-elasticity and by retardation of the relaxation processes in the region of large relaxation times. At relatively low deformation rates, the rise in viscosity and high-elasticity modulus and the retardation of relaxation processes may give way to a decrease in viscosity and high-elasticity modulus and acceleration of relaxation processes, so that stationary flow regimes are attained. The transition from strain regimes with increasing viscosity and modulus of high elasticity to those with a decrease of these quantities corresponds to an increase in the rate of accumulation of irreversible deformation. Accordingly, a competing influence due to the orientation effect and to destruction of the network of intermolecular bonds becomes evident while stationary flow is being attained. The orientation effect must be responsible for the retardation of the relaxation processes, whereas rupture of the intermolecular network bonds results in structural relaxation accelerating relaxation processes. In contrast to shearing, during extension the orientation effect is of predominant importance. Hence in stationary flow regimes the viscosity may not only remain independent of the rate of strain, but even increase with it. In this case the contribution of the large relaxation times to the relaxation spectrum increases with increasing stress in stationary flow regimes. The fact that the longitudinal viscosity and the modulus of high elasticity are independent of the stress in stationary flow regimes does not guarantee linearity of the mechanical properties of the polymer in the prestationary stage of deformation when complex changes occur in its relaxation characteristics. At high deformation rates the viscosity and the modulus of high elasticity keep rising with increasing deformation until rupture occurs. Determination of the strength of polystyrene samples vitrified after extension showed that it is due not to the entire degree of extension, but only to the value of accumulated high-elastic deformation. The strength of the vitrified samples is to a first approximation independent of the rate at which the melt was extended.
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    URL: http://dx.doi.org/10.1002/pol.1970.160080501
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    Dielectric relaxation in ethylene-methacrylic acid copolymers and their salts (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 727-738 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation data have been obtained for two ethylene-methacrylic acid copolymers (containing about 4 mole-% methacrylic acid units and about 8 mole-% methacrylic acid units, respectively) and the lithium, sodium, and calcium salts prepared by partial neutralization of the polyacids. The frequency range employed was from 50 Hz to 10 kHz and the temperature range was from -130°C to 100°C. Attention is focused on three dielectric loss regions labeled β, β and α in order of increasing temperature. The β′ process (-10°C at 100 Hz in the salts only) correlates with a mechanical loss process previously reported and is attributed to microbrownian motion taking place in an amorphous hydrocarbon phase. The β′ process (20°C at 100 Hz) has also been observed mechanically and is attributed to the same mechanism as the β process. The higher temperature of this relaxation compared to the β relaxation is attributed to the presence of acid groups which form crosslinks composed of interchain hydrogen bonds. The α process (〉50°C at 100 Hz in the salts only) correlates with dielectric and NMR data previously reported for a sodium salt and is assigned to motions within ionic domains formed by the clustering of salt groups.
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    Molecular weight distribution functions for styrene-acrylonitrile copolymers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 807-811 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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    Announcement (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 815-816 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/pol.1970.160080515
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    Determination of thermodynamic parameters of polymer-solvent systems from sedimentation-diffusion equilibrium in the ultracentrifugePresented in part at the Microsymposium on Macromolecules, “Polymer Gels and Concentrated Solutions,” Prague, September 1967. (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 841-868 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sedimentation equilibrium in the ultracentrifuge means that there is such a distribution of molecular species throughout the cell, that the centrifugal forces are balanced by differences in the activities. This provides a method for determination of the activities and the chemical potentials in polymer solutions which, in principle, is very simple and reliable. A complication is caused by polydispersity of the dissolved polymer. If one assumes that the interaction parameter depends on concentration and temperature, but not on molecular weight, it is possible to determine the chemical potential of polymer and solvent from the ultracentrifugal data. Experiments have been carried out on the systems polystyrene-toluene and polystyrene-cyclohexane at different temperatures and in the concentration range 0-80 wt-%. The results are expressed in the data for the chemical potential of the solvent, the number average chemical potential of the polymer and the interaction parameter χ.
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    Topologically interpenetrating elastomeric networks (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 921-935 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several partially interpenetrating polymeric networks (IPN) were made by combining chemically different linear elastomers. The polymer combinations were deposited as films from aqueous emulsions made by mixing the individual emulsions in equal proportions. The films were crosslinked to form two superimposed networks. In two cases, the networks were cleanly separated by hydrolysis of one of the component networks to demonstrate that there was no chemical interaction between the polymers. Measurement of crosslink density showed that, in most cases, partial interpenetration does occur as evidenced by an effective crosslink density of the IPN's greater than the arithmetic mean of the crosslink densities of the component networks. The swelling ratios, densities, and stress-strain properties were determined. For one of the network combinations, a poly(urethane-urea) and a poly(butadiene-acrylonitrile), a series of IPN's varying in polymer composition was made. The swelling ratios and densities are close to the arithmetic means; however, both the tensile strength and crosslink density exhibit a maximum at about 70% poly(butadiene-acrylonitrile). The maximum tensile strength is actually significantly higher than that of either of the component polymers. The elongations all approach that of the poly(urethane-urea), the more extensible material, except for compositions approaching 100% poly(butadiene-acrylonitrile), which exhibit a very low extensibility.
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    Wide-line proton magnetic resonance spectra of some cellulosesPresented in part at the 9th Cotton Utilization Research Conference, New Orleans, Louisiana, April 30, 1969. (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 969-977 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic wide-line proton magnetic resonance absorption spectra of a number of representative cellulose preparations have been obtained in the dry state and after addition of about 7% water. Line widths, second moments, spin-spin and spin-lattice relaxation times have been determined. The second moment of the absorption curve of dry cellulose was found to correlate well with the crystalline fraction for most specimens. A technique is described for determining the number of water-cellulose protons exchanging relative to the number of cellulose protons not exchanging. The reduction in absorption line width observed when water is added to cellulose is shown to be quantitatively consistent with such a proton exchange phenomenon.
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    The polymeric nature of selenium crystallization. I. Morphology and thermodynamic considerations (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1755-1772 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of selenium has been studied in light of present concepts of crystallinity in crystalline organic polymers. Spherulitic crystallization and resultant morphology were examined as a function of temperature by transmission and replication electron microscopy, electron diffraction, and optical microscopy. Evidence is given for polymer chain folding during crystallization of trigonal selenium. Theoretical thermodynamic calculations presented yield several thermodynamic values including an equilibrium melting point of 219.2°C, a fold surface energy of 337 ergs/cm2 and a lateral surface energy of 9.8 ergs/cm2.
    Additional Material: 11 Ill.
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    Gel-permeation chromatography: Examination of universal calibration procedures for polydimethylsiloxane in a poor solvent (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1803-1821 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various procedures for universal calibration in gel-permeation chromatography with polystyrene gels are examined for polystyrene and polydimethylsiloxane fractions. For o-dichlorobenzene at 138°C, experimental intrinsic viscosity-molecular weight data show that the Mark-Houwink exponents are 0.70 and 0.57 for polystyrene and polydimethylsiloxane, respectively. In principle, this difference permits a distinction between the various polymer size parameters proposed for universal calibration. An interpretation of the experimental polydimethylsiloxane calibration for o-dichlorobenzene at 138°C requires a consideration of errors in average molecular weights and errors arising from the use of average molecular weight instead of peak molecular weight. When calibration procedures utilizing hydrodynamic volume and unperturbed dimensions are examined, the difference between them is comparable with experimental error. If the Flory-Fox viscosity expression is employed, the perturbed end-to-end distance (or radius of gyration) and the hydrodynamic volume give equivalent universal calibrations. The experimental data are sufficiently accurate to show that the perturbed dimension determined with the Ptitsyn-Eizner relation does not give an adequate universal calibration.
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    Surface crystallization of polypropylene (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1545-1564 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization of compression-molded isotactic polypropylene and polyethylene is invariably spherulitic; generally, nucleation occurs randomly throughout the sample. In a special case where nucleation predominates at the surface, spherulitic growth centers become crowded and are forced to propagate unidirectionally into the bulk (transcrystallinity). Conditions for the formation of transcrystallinity have been investigated by optical and scanning electron microscopy. The occurrence of transcrystallinity is attributed to heterogeneous nucleation induced at the mold surface. To be effective, the mold surface must have a nucleating efficiency equal to or greater than that of adventitious nuclei present in the polymer. As the crystallization temperature approaches the melting point, the activity of mold surfaces is found to increase leading invariably to transcrystalline formation. The degree of activity of various mold surfaces correlates with the known activity of specific dispersed nucleating agents having similar chemical structures. Contrary to claims in the literature, the surface energy of the mold surface and temperature gradients across the melt surface do not play a primary role in transcrystalline formation of polypropylene.
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    Flow behavior of narrow-distribution polydimethylsiloxane (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1909-1916 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow behavior of α,ω-dihydroxypolydimethylsiloxanes, having a weight-average number-average molecular weight ratio of 1.1-1.2, was studied with a Cannon-Manning viscometer and an Instron rheometer. Comparison of the flow behavior of samples with narrow and broad molecular weight distributions indicated that the onset of non-Newtonian behavior occurred at a much higher shear rate for narrow-distribution polydimethylsiloxanes than for polydisperse polydimethylsiloxanes. A plot of reduced viscosity versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma \eta _0 {M \mathord{\left/ {\vphantom {M T}} \right. \kern-\nulldelimiterspace} T} $\end{document} gave two experimental master curves, one for polymer of narrow distribution and the other for polydisperse polymer. The experimental master curve obtained from the narrow-distribution polymer was found to fit the theoretical master curve derived from Graessley's entanglement theory. The viscosity-molecular weight relationship for the higher molecular weight polydimethylsiloxanes was found to be the same for both hydroxydimethylsilyl- and trimethylsilyl-endblocked polymers. However, at low molecular weight, the viscosity-molecular weight curve deviated from linearity because of the association of polydimethylsiloxanols, which apparently is not significant at higher molecular weights. The critical molecular weight of entanglement, Mc, was found to be about 30,000.
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    Effect of birefringence on the scattering of light. II. Oriented polymers (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1937-1953 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been considered for some time that the presence of birefringence in an oriented polymer must affect the light-scattering behavior. Previous analyses of this phenomenon are restricted to single-particle scattering. A more complete theory of the effect of birefringence on the scattering of light from correlated systems is presented. The measured scattering intensity is shown to be dependent upon the optical properties of the sample as well as the experimental technique and conditions.
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    Definition and proper usage of the various components in light scattering (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2029-2032 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    Solution of Fujita's equation for equilibrium sedimentation by applying Tikhonov's regularizing functions (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2039-2050 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Fujita equation relating molecular weight distribution to concentration of solution subjected to centrifugal forces in equilibrium proved to be an improperly posed problem in the Hadamard sense. Application of Tikhonov's regularizing functions leads to a good approximate solution of Fujita's equation. Such functions have been applied to a monomodal and a bimodal molecular weight distribution, and approximate results have been computed.
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    Structure and properties of a styrene-butadiene-styrene block copolymer (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2095-2103 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron-microscopic texture and physical properties of a styrene-butadiene-styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at -70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.
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    Thermal history and melting behavior of poly(ethylene terephthalate) (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2141-2151 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low molecular weight poly(ethylene terephthalate) samples were crystallized isothermally at 120-245°C from both the amorphous state and the melt. Isothermal annealing of these polymers at 215°C provided polymers which exhibited multiple melting peaks in thermal analysis, referred to as form I and form II, as assigned by Bell and Dumbleton. In these samples the peak temperature of the form II melting endotherm and the average crystallite size are dependent on the temperature of initial crystallization. This result requires a mechanism for retaining some structural feature during the conversion from morphological form I to form II. DSC thermograms obtained at varying heating rates on samples showing only form II endotherms support the assignment of superheating as the cause of the shift to higher peak temperatures with increasing heating rate.
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    Determination of solubility coefficients from diffusion time lags (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1411-1412 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080812
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    Self-seeded crystallization and its potential for molecular weight characterization. II. Experiments on narrow fractions (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1457-1465 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect upon seeding behavior of adding well characterized fractions has been studied, so as to assess the technique as a measure of small amounts of high molecular weight. The material available to us restricted the study to fractions with comparatively low average molecular weights. Self-seeding is shown to be an extremely sensitive measure of high molecular weight tails. Knowledge of the molecular weights concerned enabled estimates to be made of the weight of molecules involved in seeding. Instability of seeds has been observed, and is explained in terms of a particular amorphous crystalline “equilibrium” within the seeds.
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    Low-angle light scattering of ionotropic gels (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1043-1053 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-angle light-scattering patterns were obtained on ionotropic gels formed by the diffusion of Ca++ into a polygalacturonate sol. Near the sol-gel boundary, diffraction patterns were obtained which indicated organized structures with repeating units of 1100, 250, and 12.5 μ. Microscopic investigations confirmed that at this gel boundary capillaries run parallel to each other and perpendicular to the direction of diffusion. The diameter of capillaries was 12 μ while their length was in the 1000 μ range. Short interconnecting capillaries were about 200-300 μ in length. Inside the gel, in the more highly crosslinked parts, a disorientation occurs during the aging process with the partial disappearance of capillaries. However, at the gel-sol and gel-semipermeable membrane boundaries, the highly organized structures remain even during prolonged aging. The kinetics of the gel formation was also investigated.
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    Lamellar and interlamellar structure in melt-crystallized polyethylene. II. Lamellar spacing, interlamellar thickness, interlamellar density, and stacking disorder (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 85-114 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the small-angle scattering power and the degree of crystallinity in melt-crystallized high-density polyethylene have been used to evaluate the “amorphous” density in situ by the relation, \documentclass{article}\pagestyle{empty}\begin{document}$ (2\pi/V)\int_0^\infty {S\tilde g} (S)dS = (\rho_{\rm c} - \rho_{\rm a})^2 \upsilon_{{\rm er}} (1 - \upsilon_{{\rm er}}) $\end{document} where V is the irradiated volume and ḡ(S) is the “slit-smeared” absolute intensity. The amorphous density is a function of sample history and is always higher than the extrapolated melt density. After slit-height correction, and within the experimental error, the ratio of the two observed long periods is 2:1 at all temperatures (25--126°C). The lamellar thickness and the average interlamellar spacing are obtained from the degree of crystallinity and the first corrected long period. At increasing temperatures between 25°C and 110°C, the lamellae become thinner while the interlamellar zone expands by almost half. Over this range the changes are reversible with temperature. Above 110°C, both the lamellae and the interlamellar region expand with temperature. The thickening is partially reversible upon recooling. Other results obtained include measurements of stacking disorder and of microstructural changes with crystallization temperature and with time at ambient temperature.
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    Planar organosilicon polymers (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 143-160 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Work on two sheet organosilicon polymers, one derived from the mineral chrysotile and the other from the mineral apophyllite, is described. This work provides direct evidence that both these polymers are composed of sheets. In addition, it shows that in the chrysotile-derived polymer the sheets curl into scrolls, and that in the apophyllite-derived polymer the sheets are essentially flat.
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    Viscoelastic behavior of low molecular weight polystyrene (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 209-243 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear creep and creep recovery behavior of narrow molecular weight distribution polystyrene samples of low molecular weight, 1.1 × 103, 3.4 × 103, and 1.57 × 104 are reported as a function of temperature, near and above the glass temperature. Time-temperature equivalence for the total creep compliance is found to be nonapplicable, and in fact the steady-state recoverable compliance, Je, is a strong function of temperature. The time-scale shift factors for the recoverable compliance are analyzed in the light of free volume theory. Viscosity data are presented for samples with molecular weights between 1.1 × 103 and 6.0 × 105. The temperature dependence of the characteristic time constant ηJe can be explained in terms of free volume concepts whereas that of viscosity η cannot. Effects of residual molecular weight heterogeneity are demonstrated.
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    Scattering of light by deformed three-dimensional spherulites (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 295-311 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical calculation of the Hv light-scattering patterns for deformed three-dimensional spherulites is presented. Affine deformation is assumed. The optic axis of the scattering element is allowed to lie at an arbitrary angle ß to the radius which is permitted to change in the course of the deformation in a manner that may depend upon the angular location in the spherulite. The consequences of twisting of the optic axis about the spherulite radius are also explored.
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    Adsorption of polydimethylsiloxanes from solution on glass (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 331-343 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of polydimethylsiloxane polymers from solution on glass has been studied. The amount of polymer adsorbed depends markedly on the solvent because of specific solvent - surface interactions. The presence of silanol groups in the polymer, particularly as endgroups, markedly increases the amount of polymer adsorbed. Large differences are shown between the adsorption of the commercially available, and fully trimethylsilylated polydimethylsiloxanes of narrow molecular weight distribut on. Possible adsorption mechanisms are discussed.
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    Composition equation for block copolymers (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 383-384 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1971.160090214
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    Long-chain branching in low-density polyethylene (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 421-430 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is given for the analysis of long-chain branching in polymers by using combined GPC and intrinsic viscosity measurements. A computer program was written to evaluate branching indices by a tabular, iterative method. The method was applied to the evaluation of long-chain branching in low-density polyethylene.
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    URL: http://dx.doi.org/10.1002/pol.1971.160090303
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    Side-chain relaxation in stereoregular poly(isobutyl methacrylate) (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 431-435 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of stereoregularity on the low-temperature relaxation processes were studied by dynamic mechanical measurements on isotactic and syndiotactic polyisobutyl methacrylates (iso-PiBMA and syn-PiBMA). The α, β, and γ relaxation processes were observed in both stereoregular forms. Both the α, and β loss peaks were at lower temperatures for iso-PiBMA than for syn-PiBMA. The γ loss peak was observed at about -155°C at 30 Hz for both forms, and the apparent activation energy of this process was same for both samples within experimental error (6.7 ± 0.5 kcal/mole). It was reduced from these results that the α and β processes are both considerably influenced by the isotactic configuration but the γ process is not.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1971.160090304
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    Adhesion of high polymers. II. Wettability of elastomersPaper presented before the Polymer Division, 152nd American Chemical Society Meeting, New York, September 1966. (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1103-1118 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on wettability of elastomers should be considered basic to the understanding of all phases of elastomer adhesion. However, no such data in the form of critical surface tensions were available for elastomers other than polydimethylsiloxane. For this study, 18 elastomers were selected to determine the effects of functional groups, of geometrical and structural isomerisms, of copolymerization, and of the induced orientation upon wettability. Most results support the constitutive law of wettability established by Shafrin and Zisman. The effect of structural isomerisms in the form of a vinyl side group and cyclization is discussed. An equation for the calculation of critical surface tension of a copolymer or of a mixture of isomers is proposed as follows: \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _c {\rm (copolymer or mixture of isomers)} \simeq \sum\limits_1^\infty {N_i \gamma _{c_i } } $\end{document} where Ni is the mole-fraction of the individual monomer in the copolymer and \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _{c_i } $\end{document} is the critical surface tension of each homopolymer. Most elastomer adhesion studies conducted in the past were concerned with the diffusion theory of adhesion. This study further supports the conclusion on the role of diffusion and adsorption in adhesion advanced in Part I, especially with respect to the physical state of polymer at the time of application. The wettability data in this study could shed some light upon major basic mechanisms involved in elastomer reinforcement.
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    Viscoelasticity of textile fibers at finite strains (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1119-1144 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data obtained from stress-strain curves of five different textile fibers, at a series of different, constant strain rates covering a range of 61/2 decades have been used to study two methods of nonlinear viscoelastic analysis proposed elsewhere. According to the first of these, time and strain effects are factorizable so that stress σ, strain ε and time t are related by the equation σf1(ε)/ε = f(t),. This is shown to be unsatisfactory with the present materials, but an empirical modification to σf1(ε)/ε = f2(ε) + f(t) is satisfactory. According to the second, general nonlinear viscoelastic behavior can be described by an equation which reduces to the form σ/ε = F1(t) + εF2(t) + ε2F3(t) + when applied to extension at a constant strain rate. This series is shown to be strongly divergent except at fairly small stains. In fact, if it is truncated after about three terms, which are as many as can be estimated with any significance in the present experiments, it is applicable only to strains of about 3-4% and less. Numerical techniques which enable standard statistical procedures to be used have been devised to perform the above analyses and are described in detail.
    Additional Material: 19 Ill.
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    Déformation plastique des hauts polymères vitreux soumis á un système de contraintes quelconque (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1145-1156 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of rate processes has been applied by Eyring to the plastic flow of solids, but he considers only the case of simple shear. Some assumptions concerning a generalization of this theory for an arbitrary strain tensor are here proposed and discussed. The components of the deformation and the work done by the deviator of the stress during the elementary flow process are evaluated. According to these results, it can be proved that the yield condition of Huber, Hencky, and von Mises is valid when there is no hydrostatic stress. The discrepancy between the yield stresses corresponding to tensile and compressive tests is explained by the influence of the hydrostatic component and evaluated by taking account of the amount of free volume required for an elementary jump. The calculated value agrees with the experimental data. Measurements of the inclination of Lüder's bands and deformation components on poly(vinyl chloride) flat bars strained by tensile tests are in good agreement with the proposed theory.
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    Anisotropy of the mechanical loss tangent of drawn polyacrylonitrile film (1967)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1317-1319 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1967.160050629
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    Optical studies of the stress-induced crystallization of rubber (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1-30 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-angle light scattering by films of stretched natural and synthetic rubbers was investigated. Intense Vv scattering is found under conditions when crystallization occurs which is characteristic of the scattering from aggregates of dimensions comparable with the wavelength of visible light. These were identified with the γ fibrils described by Andrews. The dependence of scattering was studied as a function of light polarization direction, orientation direction, elongation, temperature, degree of swelling, type of swelling liquid, and degree of crosslinking. It was concluded that the scattering unit consists of an assembly of crystals with their chain axes parallel to the stretching direction, but (in the case of natural rubber at high elongations) with the fibril axis at a slight angle to the stretching direction. The scattering is not affected much by swelling but is decreased upon increasing the temperature. Upon recooling the scattering returns, but does so over several hours, indicating that much of the scattering arises from secondary crystallization.
    Additional Material: 23 Ill.
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    Statistical thermodynamics of polymer solutions. VI. Comblike branched molecules with branches placed randomly along the backbone (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 63-89 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermodynamic interactions between arbitrarily branched flexible “comb” molecules (with branches of uniform length affixed to backbones of uniform length but with the number of branches on a molecule and their placement arbitrary) are treated by Zimm's perturbation method to obtain results valid to the double contact approximation. Thus, bimolecular cluster configurations with one and two intermolecular contacts, but not more, are correctly accounted for. This general result is applied to “random” combs (with the number of branches per comb uniform, but the placement random) and to “heterogeneous” combs (with both the number of branches on a molecule and their placement random). Results for the random combs are very similar to those reported earlier for “symmetrical” combs (with f uniform branches disposed at points along the backbone chain so as to subdivide it into f + 1 equal sections), but the second virial coefficient for the random model is slightly the larger when the number of branches per chain is small and the fraction of the molecule in the backbone is at least a few per cent. Since random combs are uniform in mass, the osmotic pressure and light-scattering second virial coefficients are alike; but for a system of heterogeneous combs the virial coefficients differ from one another, and from the random comb result, when the mean number of branches f̄ per chain is small and they are of appreciable length in comparison to the backbone. This behavior reflects the heterogeneity in both molecular mass and dimensions existing under these circumstances. As f̄ increases and/or the mean fraction of segments in the chain backbone becomes large, coincidence with the random comb result is approached. The double-contact second virial coefficients for both random and heterogeneous combs are obtained in closed analytical expression that are much more easily reduced to numerical results than the expression for symmetrical combs given earlier. These two models also correspond better than the symmetrical combs to materials actually obtainable.
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    Narrow molecular weight distribution poly(styrenesulfonic acid). Part I. Preparation, solution properties, and phase separation (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 599-610 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described for the conversion of polystyrene to poly(styrenesulfonic acid) without change in the molecular weight distribution; the reaction is performed at room temperature in 100% H2SO4 and uses Ag+ catalyst. The resulting polyelectrolyte has solubility and other characteristics significantly different from those of previously investigated poly(vinylsulfonic acid). This permits a study of the influence of the aromatic group on the local and long range interactions in solution. The barium salt of poly(styrenesulfonic acid) is unusual in showing both upper and lower consolute temperatures in solution.
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    URL: http://dx.doi.org/10.1002/pol.1966.160040405
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    Epitaxial crystallization of homopolymers on single crystals of alkali halides (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 611-629 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial deposition of homopolymers from solution [polyethylene, isotactic polystyrene, poly-3,3-bischloromethyloxacyclobutane (Penton) and polypropylene] was found on the (001) faces of cleaved alkali halide single crystals. Electron and optical microscopy studies have shown that the polymer usually grew from small, rodlike crystallites which were oriented in (110) directions of the halide crystal. Large oriented, four-leaved, “rose” structures also were observed for polyethylene. Electron diffraction studies indicate that the polymer chain axes for polyethylene, isotactic polystyrene, and Penton generally lie parallel to the (001) faces of the halide crystal and are also oriented in the 〈110〉 directions of the crystal face. Investigations on the effect of various halide substrates upon the epitaxial crystallization habit of polyethylene inferes that lattice matching does not play the major role in orientation. Two possible explanations are offered for this epitaxial behavior.
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    URL: http://dx.doi.org/10.1002/pol.1966.160040406
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    Effect of molecular weight upon the heterogeneous nucleation of crystallization in polypropylene (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 631-638 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of basic aluminium dibenzoate upon the supercooling of polypropylene fractions of molecular weight 9.2 × 103-1.25 × 106 was determined by differential thermal analysis. The response to heterogeneous nucleation within the precision of the method used appears to be only slightly dependent, if at all, upon the molecular weight of the polymer.
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    Wideline NMR studies of oriented nylon 66 (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 639-647 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wideline NMR techniques have been applied to both singly and doubly oriented specimens of nylon 66. Variations in the spectra obtained are observed for different orientations of the specimens relative to the applied field. These variations demonstrate that the zigzag chain axis is essentially parallel to the draw direction and that motion occurs in all of the sample. The motion is of two types: random in the mobile regions and rotation of segments about the chain axis in the rigid regions.
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    On the possibility of chain folding in solutions of normal paraffins and polyethylene (1968)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 451-456 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple statistical thermodynamic argument is presented in which the probability of intramolecular chain folding of normal paraffins and polyethylene in solution is examined. This possibility is based on the existence of low-energy intramolecular conformations which are stable enough to overcome the tendency of a chain molecule to assume a random arrangement in solution. Some rough estimates of the magnitudes of energetic interaction in straight-chain hydrocarbons are made to demonstrate the plausibility of this hypothesis. The experimental support for this model arises from NMR spectra of normal paraffins in aromatic hydrocarbon solvents.
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    URL: http://dx.doi.org/10.1002/pol.1968.160060302
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    Molecular weight averages of polymers as determined by density gradient centrifugation. II. Application to nylon 66 (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 663-665 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1966.160040411
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    Crystallization in poly(n-octadecyl methacrylate) monolayers (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 649-657 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics of poly(n-octadecyl methacrylate) has been studied at the air-water interface. The rate of the crystallization has been measured by the decrease in the area of monolayers with time at various temperatures and surface pressures. The crystallization isotherms have been analyzed by the general mathematical treatment of the kinetics of phase changes, and the results show linear growth to be dominant. The variation of the rate constant with temperature and pressure has been illustrated by the difference in the supersaturation defined by introducing the equilibrium pressure-area isotherms.
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    Microfibrillar textures in polymer fibers (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 668-672 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1966.160040413
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    Specific heats of poly(vinyl chloride) compositions (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 673-684 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Specific heats of plasticized poly(vinyl chloride) can be readily obtained by means of the thin foil calorimeter when the polymer is fabricated into sheet or film. The effects of temperature and plasticizer content on the specific heat and of the plasticizer content on the glass temperature are readily observed. The data may be used to estimate the glass temperatures of plasticizers where those temperatures are not readily reached by normal techniques. The specific heat at the glass temperature is approximately 0.255 for the ranges of 0-30 phr plasticizer. A definite glass transition is not observed with 60 phr plasticizer. No other transitions were observed between 200 and 400°K. The previous history of the polymer is important, as it can change the specific heat of the polymer noticeably, especially above the glass temperature. Comparison of the values listed here with those obtained by others should be made with the understanding that these samples were fabricated by extrusion and were free of observable strain. The degree of crystallinity of these polymers is very small, probably less than 10%, since none was found by x-ray diffraction. The plasticizing effect of some stabilizers was noted.
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    Persistent polarization in polymers. II. Depolarization currentsPresented in part before the 13th Canadian High Polymer Forum, Ottawa, Ontario, Canada, September 22-24, 1965. (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 697-704 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolarization currents were used to study the persistent polarization induced in polystyrene and poly(methyl methacrylate) by cooling with flow under pressure. These studies showed that the charge on electrets made by flow under pressure consists in part of a surface charge which leaks off rapidly in moist air and in part of a charge due to volume polarization which decays more slowly. The volume polymerization produced in poly(methyl methacrylate) by flow under pressure is of the same order as that produced by cooling under a voltage drop, but flow under pressure produces a larger surface charge.
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    Persistent polarization in polymers. I. Relationship between the structure of polymers and their ability to become electrically polarizedPresented in part before the 13th Canadian High Polymer Forum, Ottawa, Ontario, Canada, September 22-24, 1965. (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 685-695 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ability of various polymers to acquire persistent polarization (i.e., to become electrets) was investigated. Polarization was induced in the polymers by two methods: (a) by cooling under a voltage drop and (b) by cooling with flow under pressure. There was found to be an optimum temperature for electret formation by either method. This optimum temperature was roughly 37°C. above Tg when polarization was produced by application of a voltage drop and roughly 57°C. when polarization was produced by flow under pressure. Crystallinity and the nonhomogeneities present in blended polymers were harmful to electret formation, but a small critical amount of ionic impurity was helpful.
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    Molecular structure of polyethylene. XIII. An improved cryoscopic method for determining number-average molecular weight of polyethylene (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 705-714 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The determinations of the number-average molecular weight of polyethylene by cryoscopy has been improved, permitting precise measurements with both linear and branched polyethylenes in the molecular weight range 4,000-30,000. Improvements include a cryometer of new design, a lower-melting cryoscopic solvent containing a nucleating agent to control supercooling and rate of crystallization of the solvent, and more precise measurement of freezing point depression. Polyethylene samples are dissolved in hexamethylbenzene admixed with 0.1% of cadmium iodide, and steady-state freezingpoint depressions are measured with a thermistor to a maximum sensitivity of 5 × 10-5°C. Molecular weight measurements are reproducible to within ±10%. The cryoscopic apparatus and procedure are described in detail, and results obtained with samples of linear and branched polyethylene are presented and discussed.
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    Les polyélectrolytes à l'interface liquide-liquide (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 765-775 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behavior of films of polyelectrolytes at the water-organic liquid interface depends on the nature of the interface and the pH of the substratum. The present paper investigates the influence of these two factors on the cohesive forces between monomer units. Two polyelectrolytes were studied: poly(methacrylic acid) (APM) and poly-2-vinylpyridine (2-PVP). In the case of uncharged films, the collapse pressure decreases when the polarity of the organic phase becomes more important, whereas the term ω/kT, which appears in the theory of Motomura and Matuura, increases. A quantitative relation between the parameter ω/kT and the collapse pressure may be deduced. The behavior of the ionized surface film at different pH values is modified by the choice of the interface. However, there exists a competition between two phenomena: the dissolution of ionized residues in the substratum and the electrostatic repulsion between charges in the surface plane. Depending upon whether the first or the second parameter is more important, we observed that the surface pressure decreased or increased with the degree of ionization.
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    Axial dispersion of polymer molecules in gel permeation chromatography (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 731-743 
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    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gel permeation chromatography is an elution chromatographic process depending on the permeation of the solute through a bed of gel particles. This process is used in the estimation of molecular weight distributions of polymers, since elution occurs in decreasing order of molecular size. The eluting species, however, are not perfectly fractionated, and apparent broadening of the distribution occurs. This broadening results from an axial (longitudinal) mixing of the eluting species. Consideration of the accessible bed volume for each species permits a correction to be made for this axial dispersion. The concept was applied to heterodisperse distributions by solving the resulting simultaneous equations. A least-squares regression may be employed to utilize the experimental data most effectively. The experimental chromatogram can be described in terms of accessible bed volume and dispersion coefficient of each species together with flow rate, sample concentration, and chromatograph column geometry. The chromatogram corrected for the axial dispersion describes the molecular weight distribution more accurately than does the experimentally determined curve. The correction procedure was applied to a well-characterized polystyrene; the results of the gel permeation chromatography show excellent confirmation of the results of fractionation and of other instrumental analyses.
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    URL: http://dx.doi.org/10.1002/pol.1966.160040506
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    Effect of crosslink density on the creep behavior of natural rubber vulcanizatesPaper presented at the 36th Annual Meeting of the Society of Rheology, Case Institute of Technology, Cleveland, Ohio, October 25-27, 1965. (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 745-763 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Torsional creep measurements on four natural rubber vulcanizates, crosslinked to different degrees, were carried out in the temperature range from -50 to 90°C. This investigation complements the studies on identical samples of the stress relaxation behavior by Chasset and Thirion and of the dynamic mechanical response by Ferry, Mancke, Maekawa, Ōyanagi, and Dickie. The creep measurements reported are shown to be in agreement with the stress relaxation results. In addition to the usual temperature reduction, a superposed curve was obtained for the long time response using the apparent molecular weight between crosslinks, Mc, as a reduction variable. The variation in viscoelastic response with crosslink density is interpreted as a restrictive action of the chemical crosslinks on the transient entanglement network.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040507
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    Effect of stereosequence length on crystallization kinetics of propylene oxide polymersPresented to the Division of Polymer Chemistry, 150th American Chemical Society Meeting, Atlantic City, N. J., September 1965. (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 715-729 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization kinetics of crystalline fractions of propylene oxide polymers made with different catalysts have been studied by isothermal dilatometric and microscopical measurements. Isothermal microscopical measurements indicate that spherulite growth in these polymers proceeds from predetermined nuclei. The half time for spherulitic appearance is less than, but of the same order as, the half time for complete crystallization. Only by taking this factor into account can the dilatometric data be represented by the Avrami equation. The deviation of the crystallization isotherm from that predicted from the microscopical data using the Avrami theory is attributed to a secondary crystallization process taking place within the spherulite. Crystallization continues long after spherulites completely occupy the available volume in the polymer. By assuming that the secondary crystallization proceeds as a first-order process in the uncrystallized, but crystallizable, portions of the melt, it is shown that the crystallization isotherms can be completely described in terms of four parameters. These are: (1) the time constant for the primary crystallization process; (2) the time constant for nucleation; (3) the time constant for the secondary crystallization process, and (4) the extent of secondary crystallization. The important conclusions of these studies are: the rates of nucleation and of spherulitic growth are far more dependent on temperature than on stereoregularity; the ratio of the rate of the secondary crystallization process to that of the primary crystallization process is almost independent of temperature, but increases with increasing stereoregularity of the polymer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040505
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  • 194
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    Structure of pressure-crystallized polypropylene (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 777-788 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of polypropylene crystallized at pressures up to 5000 atm. has been studied. Upon slow cooling from the melt at 320 atm., the γ modification, previously found only in low molecular weight and stereoblock fractions, begins to appear in small amounts in addition to the normal α monoclinic form. As the pressure is increased further, a larger proportion of the sample crystallizes in the γ form until, at 5000 atm., only the γ modification is present. X-ray and DTA studies show that the γ form of polypropylene transforms to the normal α modification at a temperature only slightly below the γ melting point. Evidence is presented which favors the occurrence of a solid-state transition as a model of transformation to the α form. Results from isothermal crystallizations at low supercoolings and annealing experiments under high pressure show that the melting point of the γ modification of polypropylene is very sensitive to crystallite perfection.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040509
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  • 195
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    Molecular weight determination of polyamides by vapor pressure osmometry (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 817-825 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The vapor pressure osmometry method for determining the molecular weight of polyamides has been studied by use of the newly developed solvents. Polymers used were polycaprolactams, polyenanthamides, and polypelargonamides. The measurements were carried out with 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol as solvents at 50 and 130°C., respectively. Endgroup determinations on samples were also done in m-cresol by 0.1 N-hydrochloric acid. Reduced resistance differences (ΔR/C)0 obtained by vapor pressure osmometry at 50°C. were found to be in linear relation with the reciprocal of the number-average molecular weight determined by endgroup titrations; but anomalous results were obtained when dodecafluoroheptanol was used as the solvent at 130°C.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040512
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  • 196
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    Orientation behavior of stereoregular poly(vinyl alcohols) (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 797-816 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation behavior of stereoregular poly(vinyl alcohols) was investigated during stretching and after releasing the stress on the bulk polymers at relatively high humidity (80% R. H.) A structural model, differing from polyethylene, was proposed in which the crystallites were embedded in a considerably swollen amorphous matrix without any definite physical interaction so as to form an aggregation of crystallites, a superstructure. The crystal orientation followed, in principle, “the first borderline case” of Kratky, but with some difference from theory in orientation, while the noncrystalline orientation was represented by the freely jointed equivalent chain model of Kuhn and Grün with a value of N/γ as small as around 5. The difference between crystal orientation found and the theorietical orientation is discussed and some factors which prevented the crystal orientation are considered.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040511
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    Group motions in the glassy state of some substituted polystyrenes and poly(vinyl benzoates) (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 789-796 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical damping measurements were carried out in the range of 103-105 cps and between 60°K. and the softening point on some substituted Polystyrenes and poly(vinyl benzoates) containing different substituents (methyl groups, methoxy groups, and halogen atoms) either in the ring or in the main chain. The ortho and meta ring-substituted polystyrenes do not show any secondary mechanical relaxation in the glassy state, although all the other substituted polystyrenes, exhibit a low-temperature damping peak (δ process) (which is in some way connected with ring motions) whose height and temperature location depend on nature, position, and number of substituents. Substituents in the para position of the ring or in the α position in the backbone chain shift the δ peak of the unsubstituted polystyrene towards higher temperatures; this shift is accompanied by an increase of the apparent activation energy E*. Substitution in the β position, on the contrary, does not affect the δ peak. Analogous results are obtained for substituted poly(vinyl benzoates), which exhibit, in addition, a β relaxation effect, associated with carboxyl group motions. A very good correlation is found between the values of E* and the limiting relaxation time τ for the δ relaxation of polystyrenes and poly(vinyl benzoates), similarly substituted in the ring, indicating that the δ relaxation leads to absorption curves in the mechanical relaxation spectrum which are characteristic of the structure of the aromatic side chain.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040510
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    The equilibrium melting point of polyoxymethylene (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 827-829 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040513
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  • 199
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    Preparation and use of very tight osmotic membranes (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 830-831 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040514
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  • 200
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    Second virial coefficient of amylose acetate (1966)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 835-844 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The second virial coefficients of amylose acetate fractions have been determined at different temperatures and have been analyzed according to recent theories of second virial coefficient.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1966.160040601
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