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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 361-388 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rheological studies were carried out on concentrated m-cresol solutions of two helical synthetic polypeptides; poly-γ-benzyl-L-glutamate (PBLG; molecular weight, 150,000) and poly-∊-carbobenzyloxy-L-lysine (PCBZL; molecular weight, 200,000). Steady shear measurements were made over a range of 0.01-16,000 sec-1 to obtain steady shear viscosity and first normal stress difference. Dynamic viscosity and dynamic storage modulus were measured both by oscillatory shear between cone and plate and also by an eccentric rotating disk device over frequency ranges of 0.1-400 and 0.1-63 rad/sec, respectively. The concentration ranges were such that both liquid crystalline and isotropic solutions were investigated. The previously reported observations of an apparent negative first normal stress difference within a defined range of shear rate for liquid crystalline solutions were confirmed for the PBLG and PCBZL solutions. At high shear rates the peaks in plots of steady shear viscosity against concentration were profoundly suppressed but peaks in first normal stress difference versus concentration were not. The observation of liquid crystalline order in PCBZL/m-cresol solutions at room temperature constitutes evidence that the inverse coil-helix transition temperature is lower in concentrated solutions than in dilute solutions. The critical concentration for formation of the liquid crystalline phase was higher for PCBZL than for PBLG, despite a higher axial ratio, due to helix flexibility.
    Additional Material: 30 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 633-640 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements on the linear thermal expansivities α∥ and α⊥ parallel and perpendicular to the extrusion direction, respectively, have been carried out between -160 and 30°C for atactic polystyrene (aPS) with extrusion ratio 1 ≤λ≤ 15 and isotactic polystyrene (iPS) with 1 ≤λ≤ 7.5. For both aPS and iPS, α∥ decreases sharply with increasing λ whereas α⊥ shows only a slight increase. Below λ = 5 the anisotropy α⊥/α∥ is nearly the same for both, but α⊥/α∥ for iPS becomes much larger at higher λ. This is accompanied by an abrupt rise in crystallinity and probably results from the increase in the number and tautness of intercrystalline tie molecules. The birefringences of aPS and iPS increase with λ and have nearly the same values for λ 〈 5. At higher λ, however, there is a sharp rise in the birefringence of iPS which is probably associated with the sudden increase in crystallinity. With an aggregate model, the chain orientation function for aPS calculated from thermal expansivity is found to be in reasonable agreement with the corresponding value obtained from birefringence.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 389-400 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of initial morphology and extrusion temperature on the orientational anisotropy and conformational changes on coextrusion drawing of poly(ethylene terephthalate) (PET) have been determined by Fourier-transform polarized infrared spectroscopy. The samples were drawn from both amorphous and semicrystalline (50%) PET at 50 and 90°C. A strong influence of coextrusion drawing temperature was observed for overall chain orientation evaluated from the dichroic ratio of the 795-cm-1 band for the samples prepared from the amorphous state: this dependence was less prominent in samples drawn from the semicrystalline state. Under the same drawing conditions, the dichroic ratio for the 973-cm-1 trans band for samples prepared from the amorphous state was higher than from the semicrystalline state. Furthermore, in all samples, the relative intensity of this band was almost proportional to the degree of crystallinity. In all samples, the gauche content, evaluated from the 896-cm-1 band, decreased with increasing draw ratio. However, the dichroic ratio of this band was near unity regardless of draw ratio, initial morphology, or extrusion temperature. From these results it is considered that all gauche units in the amorphous phase are almost isotropic in the extrusion-drawn samples with overall orientation arising largely from the crystalline chains possessing totally the trans conformation (973 cm-1) in its content. In order to evaluate the deformation mechanism of the coextrusion drawing method, the relationship between the bulk and film surface orientation is also reported.
    Additional Material: 10 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1133-1145 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Films of uniaxially oriented poly(ethylene terephthalate) (PET), Mv = 81,000, have been drawn by solid-state coextrusion in the range 40-100°C surrounded by polyethylene. This is well below the PET melting temperature and in some cases below its glass transition temperature. Properties of the extrudates, such as degree of crystallinity, mechanical and thermal properties, were investigated as a function of coextrusion temperature and draw ratio (EDR ≤ 4.4). The results show that the percent crystallinity depends strongly on draw ratio, whereas its sensitivity to extrusion temperature is limited only to the highest draw ratio (4.4). On the other hand, Young's modulus was sensitive to both extrusion temperature and draw ratio, exhibiting a maximum at EDR = 4.4 and Text = 65°C. Above this temperature, moduli decrease apparently because of increased chain mobility, resulting in dissipation of chain orientation. Furthermore, changes in yield and tensile strength followed the changes in mechanical properties, suggesting that they are dominated by the same factors. The cold-crystallization temperature TCC also revealed information about the morphological changes occurring during the extrusion drawing. For samples of EDR = 4.4, TCC increased with extrusion temperature, suggesting again dissipation of orientation by thermal motions. On the other hand, TCC decreases with EDR, and a ΔTCC as high as 73°C was found. Conventional drawing of amorphous PET has been widely reported. To our knowledge this is the first time oriented PET has been prepared using the advantages of solid-state coextrusion.
    Additional Material: 13 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1147-1161 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The drawing of semicrystalline (33 and 50%) poly(ethylene terephthalate) (PET) films has been studied by solid-state coextrusion. Because of its brittleness and opacity, isotropic and semicrystalline PET film is of little practical use. Early attempts to cold-draw crystalline films led to fracture in contrast to deformation of amorphous PET. However, we have succeeded in systematically preparing films with extrusion draw ratios ≤4.4 from semicrystalline PET. In many cases, the properties of the drawn extrudates, as a function of extrusion temperature Text and extrusion draw ratio EDR, were similar to those prepared from amorphous PET. However, some remarkable differences have also been found. In the case of coextrudates prepared from isotropic 50% crystalline PET, we found that the larger the deformation, the lower the apparent resulting crystallinity. In the extreme, a 34% reduction in crystallinity after deformation was observed. For the coextrudates drawn from initially 33% crystalline PET, slightly different behavior occurred. For Text ≤ 90°C, all extrudates showed crystallinities lower than the original isotropic film, with a minimum at EDR = 3; for Text ≥ 110°C, crystallinities were slightly greater than in the original film and increased with EDR. Qualitative measurements of heats of fusion were in agreement with density gradient results for PET crystallinity. In contrast is our previous finding that extrudates from initially amorphous PET always increase in crystallinity with EDR, because of stress-induced crystallization. The results now suggest that in the Text range investigated, the initial spherulitic structure is at least in part destroyed on drawing. In addition, the percent crystallinity is revealed to be dependent on Text, with lower values at lower temperatures. Mechanical tests show that the extrudates are similar or sometimes higher in tensile modulus when compared to amorphous PET drawn under the same conditions.
    Additional Material: 14 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1815-1823 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The differential orientation of polymer chains has been measured in polystyrene (PS)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) compatible blends. Density measurements are reported as a function of binary blend composition at 23°C. Drawing was performed by solid-state coextrusion. PS/PPO blend compositions of 90/10 and 75/25 were drawn within sandwiches of polyethylene at 145°C and isotactic polypropylene at 155°C, i.e. at ca. 25°C above the glass transition temperatures of the two blends. The change in Fourier-transform infrared dichroisms on drawing these blends was measured at 906 and 1190 cm-1, corresponding to predominantly PS and PPO, respectively. The orientation of PS and PPO was observed as a function of draw ratio λ in the range 1-5; orientations increased with λ for both PS and PPO in both blends but to different degrees. Both polymers decreased in orientation with increasing PPO content. Annealing with fixed ends showed that the PPO chains disorient more slowly than those of PS. All binary systems were found to be amorphous and compatible.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1353-1365 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Billets of chain-extended polyethylene were prepared from Alathon 7050 (Mw 59,000, Mn 19,000) in an Instron capillary rheometer by crystallization at a constant pressure of 460 MPa, at a series of teimperatures from 198 to 221°C corresponding to varying degrees of undercooling. This gives chain-extended morphologies with a range of crystallinites and lamellar thicknesses. The billets were then solid-state extruded at 100°C through a conical die with 20° entrance angle up to an extrusion draw ration 23.4. Thermal behavior was studied with differential scanning calorimetry. The orientation function measured by wide-angle x-ray diffraction showed higher orientation function measured by wide-angle x-ray diffraction showed higher orientation at equivalent draw ratio when the initial billets were crystallized at lower temperatures. Drawing efficiency, defined as the ratio of molecular draw ratio (from shrinkage) to extrusion draw ratio correspondingly increases, reaching a maximum of 0.71 in our solid-state extrusion. These studies show that highly chain-extended polyethylene, i.e., with few chain entanglements, draws poorly. Drawability was improved by increasing chain entanglements by lowering the crystallization temperature. Electron micrographs of fracture surface replicas of extrudates revealed the coexistence of undeformed, tilted, partially drawn lamellae and fibrillar structure consistent with the cahange of morphologies in Peterlin's model of plastic deformation.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1173-1176 
    ISSN: 0098-1273
    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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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1697-1699 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1427-1438 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The linear thermal expansivity of poly(ethylene terephthalate) extruded at 50 and 90°C to extrusion ratios λ of 1-4.8 has been measured between 120 and 300 K. With increasing λ, the expansivity along the extrusion direction (α∥) decreases sharply, while that in the transverse direction (α⊥) shows a slight increase. For λ 〈 3, the large drop in α∥ and the accompanying increase in the axial Young's modulus E∥ can be ascribed to chain alignment in the crystalline regions and to an increase in number and tautness of intercrystalline tie chains. At higher λ, however, the crystalline orientation apparently becomes saturated, so that taut tie molecules are solely responsible for further changes in both α∥ and E∥. On the other hand, α⊥ is mainly determined by crystalline orientation for all λ, thus showing very little increase at large λ. For the highly oriented samples (λ ≥ 3), the Takayanagi model provides a reasonable description of the behavior of α∥ and α⊥.
    Additional Material: 6 Ill.
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