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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1151-1163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.
    Additional Material: 5 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    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.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1275-1278 
    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.
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  • 4
    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 NMR second moment of a uniaxially oriented sample of polyethylene single crystals in the range of temperatures from -196°C to 130°C and its dependence on the alignment angle γ between the orientation axis (preferential direction of the molecular chains) and the NMR magnetic field are presented. The experimental results are discussed mainly with respect to the high temperature relaxation, called the α process, in polyethylene. They are compared to theoretical predictions made for a number of mechanisms of molecular motion in Part I of this work. Only one of the mechanisms considered is found to be in quantitative agreement with experiment, the mechanism here referred to as flip-flop motion. This consists of thermally activated rotational jumps of the crystalline chain segment between folds around its axis between two equilibrium sites in the lattice. Each rotational jump through 180° is accompanied by a shift of the molecule along its axis by one CH2 group. The discussion of the low-temperature relaxation of polyethylene, the γ process, is based partly on the above measurements and partly on measurements of second moments for unoriented polyethylene samples varying widely in morphology and noncrystalline content. The decrease of the second moment observed with these samples between -196°C and 20°C is taken as a measure of the intensity of the γ process. A linear correlation is found between the decrease in the second moment, designated ΔS, and the noncrystalline content, 1 - αm; this can be represented by ΔS = 1.4 + 22.1(1 - αm). It is shown that neither the crankshaft mechanism not the kink mechanism is able to account quantitatively for this result. The model of a chain end moving in a vacancy fails to adequately describe the angle dependence of ΔS in oriented polyethylene single crystals. The “sandwich model” of a polyethylene single crystal, in which the crystalline core is covered by noncrystalline surface layers, is in better agreement with observations.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 957-972 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawing of linear polyethylene at 60°C. to an extension ratio of ten drastically reduces the sorption and diffusion of n-pentane, benzene, methylene chloride, and tetrachloroethylene. Methylene chloride was chosen for more detailed study. The sorption is of the normal Fickean type. It is also fully reversible in the temperature range between 25 and 45°C. if the sorbed amount is kept to below 0.5%. At higher concentrations the sample relaxes so that sorption irreversibly increases. The reversible sorption per gram of amorphous component is about 1/6 of that in undrawn polyethylene. The diffusion constant has a larger temperature and concentration dependence than in the undrawn material. At zero concentration the activation energy for diffusion is 34.4 kcal./mole and the diffusion constant at 25°C. is 8 × 10-11 cm.2/sec. as compared with 14.4 kcal./mole and 1.5 × 10-8 cm.2/sec. in undrawn PE. Cold drawing reduces the sorption sites without changing their energy content, but drastically cuts down diffusion and increases the activation energy. A smaller part of the increase of the latter is a consequence of the lower enthalpy of the amorphous material and a larger part is probably due to the increased distance between sorption sites.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 587-598 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NMR measurements on undrawn polyethylene (PE) samples in contact with a solvent such as C2Cl4 indicate an increase in the mobility of the mobile chain segments as compared to dry samples. Highly drawn PE shows no such effect. This is because Sa, the sorption per unit mass of noncrystalline material present, decreases from 20.9 wt.-% (dry basis), found for undrawn quenched PE, to 0.63 wt.-% after drawing (Sa determined at 25°C. and 0.80 vapor activity). Drawing also reduces the segment mobility according to the NMR spectrum. It is shown that these effects are caused by considerable structural changes occurring in the noncrystalline regions of PE upon drawing. Annealing of drawn PE samples at successively higher temperatures leads to a gradual relaxation of the noncrystalline regions towards the state characteristic of undrawn PE. With increasing annealing temperature Sa as well as the mobility approach values found with undrawn PE.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 587-605 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn PE of different draw ratios (ranging from 1 to 25) and thermal treatment (annealing temperature 80, 100, 110, 120, 127°C.) was treated with fuming nitric acid at 80°C. Weight loss, molecular weight, elastic modulus, and thermograms were measured for annealed and unannealed samples as a function of the treatment time and draw ratio. As a consequence of the preferential oxidation of the noncrystalline portions, there occurs initially a high rate of weight loss and a steep drop in molecular weight, followed by a lower rate of weight loss at nearly constant molecular weight. The elastic modulus stays practically constant up to the moment where the brittleness of the sample prevents further measurement. During the later period the thermograms exhibit one melting peak during the first melting. The remelt of the same sample, however, has two melting peaks with a relative intensity independent of the treatment time. That the two melting peaks are caused by two components of different molecular weights present in the sample is substantiated by fractionation. At very high annealing temperature (127°C.), two peaks appear, not only in the first melting curve of the etched sample, but also in the melting curve of the unetched material. Such an effect is the consequence of partial melting during annealing followed by new crystallization during cooling the sample to room temperature. The findings are related to the morphology of the drawn material under the assumption of preferential scission of chain loops in the amorphous-crystalline sandwich layer model.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1011-1020 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With an increasing gradient, the intrinsic viscosity of a high molecular weight polyisobutylene (M̄n = 7 × 106) in polybutene oil L.100 (ηs = 5 poise) first drops to a minimum and then rises again. The minimum occurs at β = M[η]0ηsG/NkT = 240, which is about ten times the value predicted by the dumbbell model. Such a shift to larger gradient is in good agreement with the more realistic necklace model of macromolecules in a good solvent. The increase of intrinsic viscosity after the minimum is nearly linear with the gradient and continues beyond the value at zero gradient. Experiments with capillaries of different length-to-diameter ratios yield identical flow curves so that one may exclude the possibility that the observed upturn is an artifact caused by end effects or time dependence of viscosity.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1273-1282 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The angular dependence of scattering intensity of drawn polyethylene (PE) was investigated with a small-angle Kratky camera. At constant drawing temperature the intensity drops drastically with increasing draw ratio; however, the position and the half-width of the first maximum remain nearly unchanged. The drop in intensity can be explained only by a reduction of effective electron density difference between amorphous and crystalline components. The latter contains more vacancies, and the former contains more and better packed tie molecules. This increases the average density of the amorphous layer and decreases that of the crystalline component. As the temperature of the drawing increases, the draw ratio attainable at the applied draw rate drops and the intensity of scattering and the long period rapidly increase. In addition, a second-order maximum appears, indicating a better order of lamellar stacking, in good agreement with electron microscopy. The first annealing effect is an extremely rapid increase in scattering intensity and long period. The subsequent increase is rather slow and proportional to the logarithm of annealing time. The long period in such an experiment is independent of the draw ratio; however, the scattering intensity depends on it quite strongly even after prolonged annealing.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 179-193 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to explain the observed nonvanishing limiting value of dynamic intrinsic viscosity of polymer solutions at ω = ∞ one has considered the necklace model with finite resistance to the rate of coil deformation introduced long ago by Cerf for the study of gradient dependence of intrinsic viscosity and streaming birefringence. The calculation need not take into account change of hydrodynamic interaction as a consequence of coil deformation because the experimental data are always either obtained at very low gradient or extrapolated to zero gradient so that in the experiment the macromolecule has the same conformation as in the solution at rest. The model indeed yields a finite [η]′ω = ∞ in good agreement with experiments on polystyrene in Aroclor. According to the theory [η]′ω = ∞/[η]0 decreases with increasing molecular weight as M-1 and M-1/2 for the free-draining and impermeable coil, respectively. The absolute limiting value [η]∞′, therefore turns out to be nearly independent of M, at least for small values of internal viscosity. From the observed value [η]∞′/[η0] one can obtain the coefficient of internal viscosity of the macromolecule. The value for polystyrene in Aroclor calculated from dynamic experiments on rather concentrated solutions is close to that derived by Cerf from streaming birefringence observations of polystyrene in a series of solvents of widely differing viscosity.
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