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  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 961-973 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electron microscope study of the isothermal epitaxial crystallization of PBLG on 001 cleavage surface of NaCl or KCl from 0.01% chloroform solution with various n-octane contents has shown that the epitaxial growth process could be divided in two stages. In the first stage a rapid growth of a lamellar layer 20-40 Å thick could be observed; the PBLG molecules in αhelix conformation are oriented along 〈110〉 substrate directions. The dimensions and perfectness of alignment of these lamellae along the 〈110〉 direction depends on the molecular weight of the PBLG. In the second stage of PBLG epitaxial crystallization the relatively slow thickening of some initial lamellae takes place and one can observe many types of secondary structures. With increasing thickness of the epitaxial structures and increasing molecular weight of the PBLG the degree of orientation in relation to 〈110〉 substrate direction diminishes. The two growth stages in PBLG epitaxial crystallization are related to different kinds of orienting and attracting forces of the alkali halide substrate.
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  • 102
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 23-42 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Statistical radii of gyration, second virial coefficients, and intrinsic viscosities of sharp fractions (M̄w/M̄n ≈ 1.1) of polyisobutylene (PIB) covering a wide range of molecular weight (1.6 × 105 to 4.7 × 106) were determined in isoamyl isovalerate (IAIV) at a number of temperatures ranging from 20 to 60°C, in n-heptane at 25°C, and in cyclohexane at 25°C by light-scattering and viscosity measurements. It was found that IAIV at 22.1°C is a theta solvent for PIB. Analysis of the data by the methods described in preceding papers of this series indicated that, except for minor differences, the conclusions derived from similar studies with polychloroprene, polystyrene, and poly-p-methylstyrene hold equally for solutions of the typical linear polymer investigated here. In particular, no decisive evidence for the drainage effect was found.
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  • 103
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 89-99 
    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 dissociation of a nonionic detergent, octylphenyl polyoxyethylene ether, was studied by a temperature-jump technique. A relaxation process which is concentration-dependent was observed. A linear relation between the reciprocal relaxation time and the detergent concentration above the critical micelle concentration was obtained, from which the rate constant of dissociation kn,n-1 of one molecule of detergent from the micelle has been determined. Values of kn,n-1 equal to 0.4 ± 0.05 and 73 ± 5 sec-1 at 24.8°C were obtained for detergents with 16 and 30 ethylene oxide units per molecule of surfactant, respectively, showing and increase of the rate constant of dissociation with the length of the hydrophilic-head chain.
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  • 104
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 133-150 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on tensile strength and elongation at break for a series of Viton A-HV vulcanizates are discussed. The data were obtained at various extension rates at temperatures from -5 to 230°C (25 ≲ T  -  Tg ≲ 260°C) on seven vulcanizates having crosslink densities ve (estimated from C1 in the Mooney-Rivlin equation) from 0.46 × 10-5 to 24.4 × 10-5 mole/cm3. At an extension rate of 1 min-1, an increase in ve affects the tensile strength σb (based on the undeformed cross-sectional area) and the true tensile strength σbσb (based on the cross-sectional area of a deformed specimen) as follows: σb is essentially constant at a low temperature; it passes through a decided maximum at intermediate temperatures; and it increases to a plateau at elevated temperatures. In contrast, λbσb decreases markedly at all temperatures, an exception being the most lightly crosslinked vulcanizate(s). Application of time - temperature superposition to the ultimate-property data gave log aT; its temperature dependence is that typical of nonpolar rubbery polymers. Data on the vulcanizates were compared in corresponding temperature states by plotting log 273σb/T, log 273λbσb/T, and (λb  -  1)/(λb  -  1)max against logtb/(tb)max, where tb is the temperature-reduced time to break and (tb)max is the value at which the ultimate extension ratio λb attains its maximum, (λb)max. Except for the most lightly crosslink vulcanizate, the comparison shows that 273λbσb/T and (λb  -  1)/(λb  -  1)max are substantially independent of (or only weakly dependent on) crosslink density, that 273λb/T increases with ve, and that 273λb/T ∝ ve0.6 and λb ∝ ve-0.4 at a large value of tb/(tb)max.
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  • 105
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 159-170 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decay in birefringence of glassy polycarbonate held at constant extension has been studied at 23°C, in the time-scale range 10-103 sec, up to about 6% strain. The results show that, under these conditions, the birefringence can be validly expressed as a linear hereditary integral of the strain history up to a relatively high strain level which is about 3.4% for an experimental time-scale of 100 sec. Comparison with previously obtained data on the stress relaxation behavior of the same polymer shows that, other factors remaining constant, mechanical relaxation is linear only up to about 1.1% strain. The earlier onset of mechanical nonlinearity is discussed and it is suggested that the mechanical relaxation spectrum is richer than the optical spectrum in relatively long relaxation times, corresponding to relatively slow molecular motions. It is further suggested that these slow molecular motions are accelerated first as the polymer is extended beyond the limit of linear viscoelastic behavior. The observed nonidentity between strain limits for linear mechanical and linear optical behavior is discussed in the light of current practices in photomechanical stress analysis.
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  • 106
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1097-1109 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Past differential scanning calorimetry and dielectric relaxation measurements have established that polystyrene (PS)-poly(vinyl methyl ether) (PVME) mixtures exhibit a degree of compatibility when cast from toluene, whereas they are incompatible when cast from chloroform or trichloroethylene. The present study reports that toluene-cast mixtures can be phase-separated by thermal treatment at temperatures exceeding 125°C. This is true for samples containing 20-80 wt-% PS. The temperature of phase separation varies with heating rate; isothermal heating times needed to cause phase separation increase rapidly as the temperature approaches 125°C. Reversibility of the phase separation process depends upon such factors as cooling rate, annealing time, treatment temperature, and thermal history. By annealing and/or slow cooling, all thermally phase-separated mixtures have been brought back to their original state of compatibility. That is, there is no evidence for true irreversiblity of phase separation in thermally treated samples. Quench-cooled samples remain phase-separated indefinitely at room temperature, but this is attributed to rapid cooling below the glass transition of the PS. Chloroform-cast and trichloroethylene-cast mixtures have not been brought to a compatible state by thermal treatment, even after lengthy annealing and slow cooling steps.
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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1125-1133 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Detailed studies of the fusion of natural rubber, following isothermal crystallization, has revealed a hitherto undetected low temperature transition which depends on the crystallization temperature. This transition is shown to be a melting phenomenon which is not caused by any polymorphic structural changes. It can be attributed to the formation of less stable crystallites which develop as the transition progresses.
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  • 108
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1119-1123 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinylidene fluoride) (PVF2) is currently used to form piezoelectric films. The PVF2 molecule can exist in more than one stable conformation and it has electrically polar groups making the polymer amenable to the electrification processes involved in the formation of the piezoelectric film. The two crystalline forms of PVF2 are distinguishable by far-infrared spectroscopy. Polarized far-infrared spectra (1000-50 cm-1) of uniaxially oriented PVF2 show changes in the strong perpendicular dichroism in a number of absorptions before and after being made piezoelectric. The dichroism is attributed to a structural rearrangement from a staggered trans-gauche-trans-gauché conformation to a planar zig zag conformation. In the latter conformation the permanent dipoles are oriented approximately at right angles to the surfaces of the film and result in an electrically polarized film.
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  • 109
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1145-1152 
    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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  • 110
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 339-344 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have calculated approximate profiles for the concentration gradient in velocity sedimentation of a homogeneous solute when both the diffusion and the sedimentation coefficient depend on pressure. Pressure dependence of the diffusion coefficient narrows the peak but does not seem to shift the maximum appreciably.
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  • 111
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 377-379 
    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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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 449-471 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the polycondensation of 3,3′-diaminobenzidine with 1,4,5,8-naphthalenetetracarboxylic acid (NTC) have been investigated. Polymerizations were carried out in solution in either polyphosphoric acid (PPA) or in PPA mixed with some sulfuric acid. The reaction is heterogeneous in PPA owing to partial solubility of NTC, whereas it is homogeneous in the mixed solvent. The rate of disappearance of NTC and of dicarboxylic endgroups on oligomers was followed as a function of time at several reaction temperatures. The results show that NTC is more reactive than oligomers, so that the principle of equal reactivity is not valid for the initial steps in the polycondensation reaction.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1179-1182 
    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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  • 114
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1183-1191 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an attempt to facilitate a better understanding of the role of noncrystallizable components on the crystallization kinetics, spherulitic growth rates as well as the morphology and melting behavior of isotactic polystyrene in blends with various molecular weight atactic polystyrenes (900 to 1,800,000) over a wide range of concentrations have been studied. The growth rates are uniformly depressed with increasing amounts of atactic diluent. In addition, they are dependent on the molecular weight of the added polystyrene, generally decreasing in the molecular weight ranges between 4800 and 19,800 and between 51,000 and 1,800,000. However, between these two ranges, anomalous growth rates showing a sudden increase are observed, which may be explained by an increase in the entrapment of the noncrystallizable diluent. An explanation based on morphological observations, which showed an increase in coarseness of the spherulites with increasing molecular weight of the added atactic polystyrene, is offered.
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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1193-1206 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle light scattering in Hv and Vv modes is calculated for elliptical disks with the use of an elliptical coordinate system. The method is general for all degrees of ellipticity, from a circular disk to rodlike extensions, and permits the definition of any desired dipole orientations. The solution is obtained by computer-assisted numeric integration. Two models are considered, an “elliptical” one an “affine deformation” one differing in the orientation of scattering dipoles. The calculated patterns show a significant dependence of the distribution of the scattered intensity on the size and the elliptical axial ratio in both models, permitting the determination of both the size and the degree of ellipticity of the disk from its patterns. In addition, the differences between the calculated results for the two models are sufficiently large to permit the selection of the experimentally appropriate model, at least within the range of moderate degree of ellipticity.
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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1221-1236 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallite sizes have been obtained from the breadth of equatorial x-ray reflections from polypropylene samples subjected to a draw ratio of 6 at 21°C and then annealed at 155°C, 140°C, and 120°C, respectively. For all samples it was found that the ratio of the dimension of the crystallite perpendicular to the {110} planes to that perpendicular to the (040) plane is a constant. The ratio of the lateral crystallite size to the meridional long period was also found to be constant, independent of annealing temperature. In contrast, the thickness of the crystallites in the direction parallel to the draw direction, as calculated from the meridonal long period and density data, was not proportional to the lateral crystallite size.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1237-1254 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray scattering (WAXS) patterns of two polypropylene samples, a quenched sample drawn at 21°C and an annealed sample drawn at 100°C, were investigated in a range of values of draw ratio λ very closely spaced through the neck region. In both cases, a range of small λ where deformation occurred by spherulite deformation was followed by one of higher λ where microfibrils were formed. The contribution to the WAXS pattern of microfibrils could be clearly distinguished from that of deformed spherulites because of the better orientation parallel to the draw direction of the former as compared to the latter. Additionally, for a drawing temperature of 21°C, microfibrils crystallize in the “smectic” phase as compared to the monoclinic phase for the initial sample and deformed spherulites. At this temperature, plastic deformation proceeds through the spherulite deformation mechanism up to λ = 1.4 accompanied by an increase in chain orientation with increasing λ. For λ 〉 1.4 plastic deformation appears to occur exclusively through microfibril formation. For drawing at 100°C, spherulite deformation is accompanied by very little change in chain orientation up to λ = 2, where microfibril formation begins. For λ 〉 2 (Td = 100°C) plastic deformation is accompanied by both microfibril formation and some spherulite deformation as reflected by changes in both orientation and crystallite size. At this temperature the lateral crystallite size in the microfibrils is related to the long period according to the “equilibrium crystallite shape” previously found for annealed polypropylene.
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  • 118
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 721-740 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An unsaturated polyester resin and the styrene-crosslinked polyester were studied with laser Raman spectroscopy. Following the polyesterification reaction, Raman measurements showed that the polyester contained 55% fumarate and 45% maleate unsaturation. Additionally, the glycol fragment was indicated to exist as the gauche isomer. The 1213 cm-1 line is assigned to the glycol-ester linkage and can be measured to follow the conversion to polymer. After the crosslinking reaction, styrene was found to copolymerize preferentially with the fumarate unsaturation. There was no evidence of forming long-chain polystyrene crosslinks. Our results indicate that, after crosslinking, 41% of the fumarates have reacted with styrene and there is an average of two styrene molecules in each link.
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  • 119
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 769-779 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements are reported of the solubility and concentration of propane and propylene in polyethylene, at temperatures from -30°C to +30°C and pressures from 1.68 to 3.52 atm. Solubility of both gases in polymer depends on penetrant activity. Henry's law is not obeyed at high values of the penetrant activity, i.e., in the vicinity of the condensation point of the gas. The interaction between the solvent and the polymer is independent of pressure and a function of temperature. The propylene-polyethylene interaction seems to reach a maximum at 10°C within the range investigated. A physical mechanism, based on opposite effects of temperature upon polymer and penetrant, is suggested to explain the results.
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  • 120
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 835-845 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From thin films produced by vacuum evaporation and condensation of polyethylene, single crystals were grown by subsequent heat treatment of the films in xylene. Extended molecular chains composing the crystals are approximately 150 Å in length, i.e., about 1.5 times the thickness of the crystal layers. Electron microscopic examination of the crystals revealed that they were morphologically similar to ordinary polyethylene and paraffin single-crystals, e.g., they sometimes exhibited a hollow pyramidal shape or typical spiral growth.
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  • 121
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1207-1219 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilatometric, calorimetric, and dissolution studies have been made of two crystalline modifications of trans-1,4-polyisoprene in order to determine their equilibrium melting temperatures. This parameter is of fundamental importance in the formal treatment of polymorphism in crystalline polymers. A consistent set of thermodynamic parameters has been derived for both crystalline modifications. The equilibrium melting temperature of the polymorph, which was previously observed to melt from carefully crystallized bulk material at 64°C, was calculated to be at least 82.4°C. The other form, which melts from the bulk at 74°C, has an equilibrium melting temperature of 79.5 ± 0.5°C. The trans-1,4-polyisoprene, crystallized by stirring n-butyl acetate solutions at 49°C, was found by x-ray diffraction to be in the first form and melts at 81.2 ± 0.5°C when very slow heating rates are applied. This melting temperature is very close to the independently derived equilibrium melting temperature and lends support to the possibility that extended chain crystals are present in these solution crystallized crystals. Using the newly found melting temperatures of the two crystalline modifications it can be derived from the free energies of fusion that the first crystalline form is more stable at temperatures above approximately 66°C, whereas the other form is more stable below this temperature.
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  • 122
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1273-1283 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The two endotherms found during DSC analysis of annealed or drawn poly(ethylene terephthalate), PET, are discussed in greater. detail. Earlier workers proposed that the endotherms were the result of separate morphologies, i.e., extended-chain and folded-chain crystals, but more recently Roberts and others have presented data on the effect of DSC heating rate on annealed PET endotherm areas which indicate that the higher temperature endotherm is the result of recrystallization in the DSC. The present work explains the reasons for recrystallization, and presents data showing that samples cooled at various rates from the melt also exhibit recrystallization in the DSC, in much the same manner as samples annealed for different lengths of time. Further, by prolonged annealing before analysis, part of the recrystallization exotherm can be observed in the DSC scan. Drawn nylon 66 also exhibits recrystallization in the DSC, in a manner similar to annealed or slowly crystallized PET. The amount of material that recrystallizes is determined by the time and supercooling available between first melting and the ultimate recrystallization temperature, i.e., a temperature at which there is too little time and temperature driving force for further recrystallization to occur. Infrared absorption data show an increase in “regular” fold content during prolonged annealing of PET, while dynamic mechanical data show a marked decrease in a dispersion that is likely associated with the looser fold crystal morphologies. Annealed PET does superheat in the DSC, leaving unanswered the question as to whether any partially extended material is present along with the regular-fold material. For cold-drawn PET, the infrared data indicate disappearance of regular folds and the dynamic mechanical data indicate disappearance of the looser folds. Cold-drawn PET also superheats. These data indicate a likelihood of at least partially extended morphologies in cold-drawn PET; these observations do not apply to PET drawn at high temperatures or to polyethylene.
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  • 123
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1297-1304 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition temperature of systems based on epoxy resin and a number of diamines has been determined by using a torsion pendulum. An equation relating composition and crosslink density with the glass transition temperature has been established which gives reasonable predictions of the glass transition temperatures for systems based on aliphatic or aromatic amines and methylated amines and for systems containing a monofunctional epoxy diluent. The equation may be used to predict Tg for systems with non-stoichiometric quantities of curing agent and blends of amines. Deviation of the predicted and observed values for Tg is interpreted in terms of differences between definitions of Tg used by other workers and, also the occurrence of competing side reactions during polymerization which lead to additional crosslinks.
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  • 124
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1305-1319 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of nylon 6 from 4.2 to 300°K was investigated as a function of orientation, anisotropy and moisture content by using an inverted free-oscillating torsion pendulum. Three new relaxations, δ at 53°K, ∊ below 4.2°K, and ζ at 20°K, were discovered. The characteristics of these new relaxations strongly depend on the orientation anisotropy, and concentration of adsorbed water in the specimens. The results suggest that the mechanism of the γ process is associated with the motions of both the polar and methylene units. The mechanism of the β relaxation is postulated to originate with motions of both non-hydrogen-bonded polar groups and polymer - water complex units. The behavior of the α peak is consistent with the hypothesis that it originates with the rupture of interchain hydrogen bonding due to the motions of long-chain segments in the amorphous regions. Finally, the data strongly support the proposition that two types of water, tightly bound and loosely bound, exist in nylon 6.
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  • 125
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1337-1349 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two types of emulsion-grade polytetrafluoroethylene particles have been studied. We refer to these as ribbons and rods. The ribbons consist of very thin ribbons or lamellae folded upon themselves a number of times. In typical emulsion-grade material prepared at Allied Chemical, the unraveled ribbon measures about 3.25 μ in length, 0.25 μ in width, and 60Å in thickness. The folded ribbons, which form the particles, are about 0.5 μ long and 0.25 μ wide. Electron diffraction shows that the ribbons are single crystals with the chain axis parallel to the long axis of the ribbons thus forming extended chain crystals. This extended-chain packing is consistent with the observed cleavage or fibrillation of the ribbons and with the molecular weight. The rods are formed in low-yield polymerizations. Electron diffraction also shows that the rods are single crystals with the chain axis parallel to the long axis of the rods. Striations parallel to the long axis are believed to result from stacking of parallel segments. Considerable bending of the long axis of rods is observed.
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  • 126
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1321-1336 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transient photocurrents in poly(vinyl chloride) films are shown to be due to photo-injection of electrons from metallic cathodes. Most of the injected electrons are promptly trapped, but some drift across the sample to the anode under the influence of an external electric field. The mobility of these electrons, determined by transient photoconductivity techniques, is 4.7 ± 0.5 × 10-4 cm2/V-sec at 27°C, and rises to 3.4 ± 0.5 × 10-3 cm2/V-sec at 43°C, the measuring cell having been evacuated to a pressure of 10-6 torr at both temperatures. Diffusion of helium into the samples appears to decrease the electron, mobility. It is suggested that electron transport is correctly described by using an energy-band model for intramolecular motion and an activated hopping model for intermolecular transfer. Oscillations observed in the transient photocurrents in the frequency range 103-105 Hz are attributed to electron avalanche formation at the anode, with photosuccessors.
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  • 127
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1361-1367 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From a model of delocalized triplet energy in an aromatic vinyl polymer, the relative efficiency of triplet-energy transfer to either an added or copolymerized quenching molecule is determined. It is found that copolymerization can increase the photoprotective efficiency only if the quenching rate is determined by the final energy transfer step. A study of the quenching of polystyrene phosphorescence by added or copolymerized naphthalene indicates that there is no enhancement of quenching efficiency by copolymerization.
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  • 128
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1351-1359 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elongational viscosity of dilute polymer solutions must always be measured under nonsteady-state conditions. To predict the time dependence of this viscosity for a polymer solution in which a constant stretching rate is maintained, a simple model is considered in which the polymer molecules are represented by elastic dumbbells. The non-Hookean elastic force in the dumbbell is determined by the conformational entropy of the chain. Use is made of Peterlin's approximation which replaces the elastic force by a function of the root-mean-square end-to-end distance. Application to the transient state is straightforward; it can be extended to include the effect of “internal” chain viscosity by means of approximations that are similar to Peterlin's.
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  • 129
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1397-1400 
    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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  • 130
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energies for (1→4)-linked α-D- and β-D-galactans have been computed by considering nonbonded, torsional, and electrostatic interactions. The electrostatic interactions are estimated by assigning the charges to various atoms in the molecule by the method of Del Re. The characteristic ratios CN = 〈r2〉0/Nlv2 are computed for α-D- and β-D-galactans as a function of the degree of polymerization N and the angle τ at the bridge oxygen atom. These values of characteristic ratios obtained for α-D-galactan are very much higher than for β-D-galactan, indicating that the former assumes a highly extended conformation compared to the latter. The values of characteristic ratios of both these polysaccharides show a decrease with increase in τ similar to that observed for other (1→4)-linked polysaccharides. The calculated values of C∞ of (1→4)-linked polysaccharides show no correlation with the number of allowed conformations but are affected both by the orientation of the interunit glycosidic bonds and the hindered potential associated with chain units. It has also been shown that the magnitude of the steric factor σ may not be used as an index of flexibility for polysaccharides which differ in type of linkage.
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  • 131
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1401-1405 
    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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  • 132
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation was made of the dynamic mechanical behavior in the rubberlike region of poly(n-butyl methacrylate) (PBuMA) and poly(n-butyl acrylate) (PBuA) networks lightly crosslinked with ethylene dimethacrylate to concentrations from 10-6 to 10-4 mole/cm3. The measurements were carried out by use of an apparatus for low-frequency forced vibrations working in the frequency range 2.5 × 10-4 to 1 Hz. With parameters c1 and c2 of the Williams-Landel-Ferry equation, obtained from data in the main transition region, the data did not reduce in the rubberlike region for the poly(butyl methacrylate) networks; the spread of the deviations decreases with increasing concentration of the crosslinking agent. Superposition could be achieved in all cases when a shift factor was used on the vertical axis. At sufficiently low reduced frequencies and at high temperatures the storage compliance decreases in both series of polymers with increasing concentration of the crosslinking agent as expected. At higher reduced frequencies and at higher temperatures of measurement, however, anomalous behavior was observed with uncrosslinked samples having a lower compliance than those crosslinked to a very low degree. This finding was explained as due to very long relaxation times of the untrapped entanglements present in the noncrosslinked polymer, which are absent in the same polymer crosslinked already to very low degrees. The retardation spectra of both PBuMA and PBuA exhibited secondary relaxation mechanisms which were shifted by four logarithmic decades toward higher retardation times in comparison with the primary retardation maximum.
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  • 133
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1407-1414 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The methods of Hermans and Weidinger and of Wakelin et al. (the correlation and integral methods) were used to determine the degree of crystallinity in poly(ethylene terephthalate) (PET) fibers. A standarization of cutting of the amorphous background scattering in PET fibers, indispensable for the method of Hermans and Weidinger, is put forward. On using a partial standardization of the intensity diffracted and scattered in the fiber, namely, on taking into account the x-ray density of the specimen, variability in the intensity due to differences in absorption in the specimen at different angles 2θ and variability in the specimen mass reflecting x-rays in the function of the diffraction angle, good agreement of the PET fiber crystallinity values is observed.
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  • 134
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1415-1445 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A reaction rate model of fracture in polymer fibers is described. This model assumes that bond rupture is governed by absolute reaction rate theory with a stress-aided activation energy. It is demonstrated that the key in obtaining good agreement between the model and experiment lies in taking proper account of the variation of stress on the tie-chain molecules. The more taut chains rupture first, and the load is redistributed among the remaining unruptured tie chains. The effect of varying the temperature both in the model and in experiments on fracture in fibers is explored. Good agreement between predictions of the model and experiment is possible only with an undeterstanding of the distribution in stress on the tie chains. The distribution in stress on the chains was experimentally determined by monitoring the kinetics of bond rupture with electron paramagnetic resonance (EPR) spectroscopy. Temperature is found to have two effects on macroscopic strength. (1) The thermal energy aids the atomic stress in breaking the atomic bonds; as a consequence the rate of bond rupture of a family of bonds under a given molecular stress is increased. In this respect temperature might be viewed as decreasing the “strength” of a bond. (2) Temperature also serves to “loosen” the molecular structure and in this way modify the distribution in stress on the tie chains. To explain bond rupture and macroscopic fracture behavior quantitatively, account must be taken of both effects.
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  • 135
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1447-1459 
    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 obtain information about a possible helix-coil transition of isotactic polystyrene (i-PS) at 80°C in toluene, as has been reported in other solvents, solution properties were examined at temperatures between 10 and 110°C. Use was made of viscometry, high-resolution nuclear magnetic resonance, infrared spectroscopy, calorimetry, and light scattering. No distinct transition was found at 80°C but rather a second-order transition between 62 and 65°C. A similar transition occurred in toluene solutions of atactic polystyrene. The transition may be attributed to a sudden change in the mobility of the phenyl side-group of the polymer. From this study it is concluded that i-PS has a helical conformation in toluene, the mean helix length decreasing smoothly with increasing temperature.
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  • 136
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1461-1465 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An explicit form of Mueller's phenomenological matrix has been derived which characterizes the small-angle light scattering from an anisotropic sphere when the requirements of the Rayleigh-Gans approximation are fulfilled.
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  • 137
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 71-87 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The modified Birnboim transducer and a computerized data acquisition and processing system (DAPS) for the measurement of viscoelastic properties of macromolecular solutions are described. The apparatus has a continuous frequency range from 0.01 to ca. 700 Hz and a viscosity range from 2 to ca. 30,000 poise (sample volume 1 to 1.5 cm2). Sample temperature is controlled to within 0.002°C from -30°C to +80°C. Working displacements are 102 to 104 Å. The DAPS is designed for precise determinations of the magnitudes and relative phasing of two sinusoidally time-varying electrical signals (0.02%, 0.02°, respectively, for signals 〉 2 V peak) from 10-2 to 105 Hz. Cross-correlation techniques are used for noise rejection. For frequencies below 30 Hz values of the storage (G') and loss (G″) components of the complex shear modulus (G*) of 1 dyne/cm2 are determined to within 10% and 4%, respectively, for liquids of moderately low viscosity. Proportionately higher measurement accuracies for typical values of G' and G″ and the wide frequency and viscosity ranges permit extrapolation to infinite dilution and studies of limited molecular flexibility for many polymer - solvent systems.
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  • 138
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 123-131 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The following quantities were measured on a number of ethylene-vinyl acetate (EVA) and ethylene-acrylic acid (EAA) copolymers: (1) the small-angle x-ray scattering invariant, (2) the overall density, and (3) the crystallinity. Assuming a two-phase structure, the separate values of the densities of the crystalline and amorphous regions can be calculated from these data. Of these, the crystalline density is compared with the value obtained from the lattice constants. A systematic difference is observed which is ascribed to the presence of comonomeric side groups in the crystalline regions. For the EVA and EAA samples, their concentration is at least 0.3 and 0.5 times the overall concentration, respectively. The amorphous densities are found to be higher than the values calculated from completely amorphous copolymers by extrapolation procedures.
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  • 139
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 201-219 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present work is a continuation of a general study of the effect of pressure on gas and vapor permeation through nonporous polymeric membranes. Permeability coefficients have been measured for 1,1-difluoroethylene (C2H2F2) and fluoroform (CHF3) in polyethylene at penetrant pressures up to 35 atm and at temperatures between -18 and 70°C. The permeability coefficient P̄ for the 1,1-difluoroethylene - polyethylene system was found to increase with increasing pressure differential Δp across the membrane. Isothermal plots of log ΔP versus Δp are generally linear and can be represented by empirical relations of the form ΔP = P(0)exp{m Δp}, where P(0) and m are constants. The slope m of these isotherms decreases with increasing temperature. Plots of log P̄ versus Δp for the fluoroform - polyethylene system are also linear, but exhibit negative slopes, i.e., P̄ decreases with increasing Δp. An extension of Fujita's “free volume” theory of diffusion in polymers shows that the dependence of P̄ on pressure reflects how the free volume of the polymer is affected by this pressure. An increase in the penetrant pressure may result in two opposing effects: (a) the concentration of the penetrant dissolved in the membrane is increased, thereby increasing the free volume, and (b) the hydrostatic pressure on the membrane is also increased, which causes a decrease in the free volume. If the overall effect is an increase in the free volume of the polymer, then P̄ will also increase, and vice versa.
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  • 140
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 239-252 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As a continuation of the preceding study on the folding behavior of short polymer chains, an iodine-terminated paraffin having 156 Å peak molecular length and a sharp molecular weight distribution was prepared. The paraffin could be crystallized in lamellae of two different thicknesses: (A) thickness close to half the chain length (the most readily obtained); (B) thickness intermediate between half chain length and fully extended chain. Case A corresponds to each chain folding once with equal stems and with ends at the surface. Degradation behavior revealed that the folds must be of closely equal length giving rise to an even fold surface. In case B the situation is more involved: here the chain ends must turn into the lattice. Adjacent reentry is a necessity throughout. In both cases the lamellar thickness could be increased by annealing up to complete chain extension.
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  • 141
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 221-238 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Short aliphatic polymer chains of different lengths were prepared by degrading polyethylene samples of appropriately chosen initial fold lengths to the chain lengths which correspond to a single chain traverse through the lamella. The resulting dicarboxylic acids were either used as such for further crystallization experiments or were first converted into diiodides to remove polar endgroups. The resulting short polymers all crystallized by chain folding even if the chains (peak of distribution) were only 1.5-4 times the length of a traverse through the lamella. In the diiodides the fold length varied continuously with crystallization temperature, as is usual in high molecular weight material, but with the dicarboxylic acids such variation, while observable, was only small. The effect of the molecular weight on the fold length due to its influence on supercooling at a given crystallization temperature has become apparent. Renewed degradation with nitric acid and subsequent GPC analysis of the degradation products confirmed the folded nature of the chains in the above crystals. This analysis combined with experiments on the reactivity of chain ends has led to the picture that each chain folds completely, once, twice etc. so that both folds and ends are in the surface zone but are located at varying heights, as appropriate to the overall layer thickness for the molecular weight distribution in question. This picture is consistent with other concurrent work.
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  • 142
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in crystal structure during polymerization and oligomerization of 2,5-distyrylpyrazine have been investigated by x-ray crystallography. The polymer and the oligomer as obtained are three-dimensionally oriented, and the directions of the three axes of the resultant crystals coincide with those of the original crystal. The space group of the products also agrees with that of the monomer. It is concluded that the polymer and the oligomer crystals approximately duplicate the molecular arrangement in the monomer crystal. The polymerization mechanism is discussed on the basis of the crystal structures.
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  • 143
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1587-1592 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure and morphology of highly oriented fibers were modified by thermal treatments at varying tensions. The structural changes were characterized by wide- and small-angle x-ray diffraction, broadline nuclear magnetic resonance, and electron microscopy of surface replicas. Increasing temperatures caused increases in local ordering, number of regular chain folds, mobile fraction or amount of fluidlike mobility, and surface recrystallization in localized areas. Each of these changes was also a function of the amount of tension on the fiber during the annealing; each change was maximized when the fiber was free to shrink but minimized when the fiber was stretched.
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  • 144
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1609-1610 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 145
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1593-1607 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory which relates the change in the strength of absorption to the change in crystal orientation function is presented for the anisotropy of dielectric relaxation for the dipolar orientation change in an oriented crystalline polymer. Experimental measurements are presented for the α dielectric absorption of a stretched ethylene-carbon monoxide copolymer and compared with the orientation of crystals of this copolymer as determined by x-ray diffraction.
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  • 146
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 499-505 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The healing of scratches on the surface of vitreous selenium was observed over a period of nine weeks, and from the data the solid surface tension of vitreous Se is estimated to be (100 ± 20) dyne/cm at 38.8°C, about the same as that of the liquid at the melting point. This value is three times as large as the critical surface tension determined from contact angle measurements, which indicates that for vitreous Se in contact with organic liquids, the solid - liquid interfacial tension is about two-thirds as much as the solid surface tension. The present method of measurement can probably be used to determine the solid surface tension of other polymers, and by measuring the healing of scratches on a solid immersed in a liquid the method could be used to determine the solid - liquid interfacial tension.
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  • 147
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 527-539 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extrema in the unpolarized and the horizontally polarized angular scattering patterns are used as a basis for size-distribution analysis of polymer latex systems composed of single, spherical, optically isotropic particles. The method of analysis is similar to that recently proposed for vertically polarized scattered light and the polarization ratio, where the modal diameter and a distribution width parameter are determined from the experimental angular scattering pattern and prepared theoretical diagrams obtained by Mie theory calculations. The method of analysis, based on all four scattering functions, is illustrated by use of a Dow polystyrene latex sample.
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  • 148
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 569-570 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 149
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sulfur-cured natural rubber and other elastomers subjected to tensile tests at low temperatures and low strain rates are found to swell and “foam” after testing when brought to room temperature. The conditions under which this phenomenon can occur are established and related to load-extension curves. Free radicals formed during tensile testing are studied by electron spin resonance (ESR) techniques. It is found that the free radicals observed at the low temperatures are stable below the glass transition temperature of the material, and it is suggested that these radicals arise from mainchain fracture occurring during yielding of the material. The subsequent swelling at higher temperatures is found to be due to the expansion of environmental gases absorbed during tensile testing and to the release of hydrogen in certain cases from the materials tested. It is also suggested that yielding of the material which gives rise to these characteristics occurs by crazing of the material; the voids in the craze bands absorbing the environmental gases which subsequently cause the foaming at higher temperatures.
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  • 150
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 657-672 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method described for the determination of molecular weight and long-chain branching distributions of polymers requires no prior knowledge of the functional relation between branching frequency and molecular weight. It is based on preparative fractionation and viscometric and gel-permeation chromatographic measurements on both fractions and whole polymer. The technique is applied to several polybutadienes and butadiene-styrene copolymers differing widely in method of synthesis and pattern of long-chain branching.
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  • 151
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical properties were correlated with glass transition temperatures for a series of random copolymers of methyl methacrylate with comonomers selected from the higher n-alkyl acrylates and N-n-alkylacrylamides. The plasticizing comonomers were the n-butyl, 2-ethylhexyl, n-octadecyl, and oleyl acrylates, and the N-n-butyl-, N-n-octyl-, N-n-octadecyl-, and N-oleylacrylamides. The complete range of compositions was investigated. However, the bulk of the data was obtained on compositions in the glassy region below the onset of the vitreous transition. In this region it was found that the decrease in tensile and flexural moduli and strengths with increase in internal plasticizer for all of the systems was directly proportional to the decrease in Tg. It was concluded that the additive contribution to the free volume made by each side-chain methylene group was alone responsible for the magnitude of the rate of change of properties. However, polar contributions of the amide group to stiffening the main chain exceeded those of the ester, so that the amides were less efficient plasticizers. An empirical equation was derived which described, with fair accuracy, the decrease in the mechanical parameters with composition for the amorphous copolymers. It was reasonably successful in predicting properties even into the composition range where the ambient testing temperature corresponded to or exceeded the transition temperature. In this transition region an accelerated decrease in the magnitude of the physical properties was observed. All samples exhibited brittle fracture except those tested in the transition region. Here the strain was largely irrecoverable flow. Side-chain crystallinity did not interfere significantly with the mechanical properties because moduli and strengths had already decayed to small values near the compositions where crystallinity commenced. Non-random copolymers of vinyl stearate and methyl methacrylate showed no internal plasticization, apparently because of macrophase aggregation.
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  • 152
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1691-1698 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Use of a new apparatus is described which enables infrared dichroism to be followed as a function of time following the rapid stretching of a sample. The apparatus is double beam in dichroism, in that the infrared beam is alternately polarized parallel and perpendicular to the stretching direction and the transmitted intensity is observed on an oscilloscope. Results are presented for the stretching of a low-density polyethylene sample by approximately 28% in a time of approximately 0.1 sec. The infrared dichroism is observed to change in times of the order of 50 to 100 msec after stretching, confirming the observation made by other techniques that crystal orientation changes during this time.
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  • 153
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1709-1717 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of high-density polyethylene were irradiated with x-rays and oxidized with concentrated nitric acid to determine the location of unsaturated groups. Vinyl groups initially present in the polymer were rapidly oxidized to the extent of 85% and are assumed to be excluded from the crystals. Vinylene groups show a rapid oxidation followed by slow oxidation. The initial oxidation is about 35%, which is slightly greater than the 25% amorphous content of the polymer prior to irradiation. Diene groups are rapidly oxidized by nitric acid but are formed at about the same rate in crystalline and amorphous samples. This is interpreted to indicate that diene groups are formed throughout the polymer but form large defects in crystalline regions and are accessible to oxidation. Defects formed in crystalline regions during irradiation lower the melting point to a greater extent than predicted by the mole fraction of noncrystallizable units.
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  • 154
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1699-1707 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fully methylated nylon 12 was prepared by the hydrolytic polymerization of N-methyllaurolactam. The polymer, with about 20% crystallinity, has a crystal structure different from that of nylon 12. The X-ray diffraction patterns of copolymers of N-methyllaurolactam and laurolactam were shown to be composition-dependent. Copolymers containing up to 15% laurolactam units exhibited a crystal structure essentially the same as poly-N-methyllaurolactam. Copolymers containing from 20 to 50% laurolactam are transition structures, whereas copolymers containing more than 50% laurolactam units exhibit a crystal structure characteristic of polylaurolactam. DSC data on the homopolymers and copolymers are also reported.
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  • 155
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1731-1741 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single crystals of polyethylene are investigated by transmission electron microscopy. A pattern of lines is observed in the crystals. The properties of these lines suggest that the lines represent slip traces (slip steps) generated by the movement of dislocations in the polyethylene crystals.
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  • 156
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1743-1748 
    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 presented for measuring the change of the intensity of x-ray diffraction peaks of cellulose specimens as a consequence of humidity changes of the specimens. Measurements performed showed a decrease of this intensity after drying pulp specimens initially kept in humid air. Thus the order in cellulose decreased during drying.
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  • 157
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1789-1797 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the crazing of glassy amorphous polymers, wetting ability and penetration of the fluid are the important practical parameters governing the activity of the fluid. Higher molecular weight and the presence of polar groups in the fluids result in an increase in the critical stress for craze initiation in polystyrene and polycarbonate. The Eyring treatment of the craze process can describe fairly well the temperature and strain rate dependence of the critical stress. The parameters involved in the Eyring theory suggest that the crazing takes place by a molecular motion of lower energy than does macroscopic yielding.
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  • 158
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1757-1774 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three types of domain structures, namely spherical, rodlike, and lamellar, of A-B and A-B-A (or B-A-B) block copolymers cast from solutions are discussed on the basis of a criterion that the structures originate at a critical micelle concentration as a result of microphase separation of the block segments and the micelles formed maintain their structures into the solid state without reorganization. It is concluded that the micelles shrink mostly in the direction perpendicular to the interface between the two phases within the micelles because of the appreciable orientation of the block segments in this direction. In other words, the spherical micelle shrinks isotropically to form a spherical domain having a diameter proportional to the 2/3 power of the degree of polymerization (molecular weight) of the corresponding block segment. Rodlike and lamellar micelles, on the other hand, shrink anisotropically to form rodlike and lamellar domains such that the diameter and the thickness of the respective domains are roughly proportional to the 1/2 power of the degree of polymerization of the corresponding block segment.
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  • 159
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1811-1836 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model for the crystallization kinetics of polymers is outlined and is used to interpret observations of the crystallization of polyethylene at high pressures. This model introduces a distinction between σe the lamellar surface energy which controls the lamellar thickness, and σe′, the surface nucleus surface energy which controls the growth rate. Differential scanning calorimetry and electron microscopy data for several polyethylenes crystallized at pressures of up to 8 kb are presented. From the dependence of lamellar thickness on the crystallization undercooling at 5 kb, it is found that σe increases markedly with pressure leading to the formation of very thick crystals at high pressures. The magnitude of the increase in σe is in agreement with σe values calculated from the dependence of melting temperatures on pressure. The nucleus surface energy σe′ is not expected to vary significantly with pressure, and estimates of growth rates of 5 kb which indicate that the growth rate does not vary significantly with pressure at constant under-cooling confirm this. Fractionation effects and the differences in behavior between different polyethylenes are also discussed.
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  • 160
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1841-1844 
    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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  • 161
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1845-1848 
    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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  • 162
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1849-1851 
    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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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1931-1939 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to study the effect of the molecular weight on the crystallinity and conformational changes of poly(β-benzyl L aspartate) in films, a previous study on high molecular weight samples has been extended to included polymers of low molecular weight, about 3.3 × 103. Films were prepared from chloroform solution by quick or slow evaporation at room temperature. The conformation and the thermal behavior were studied by means of infrared spectroscopy and differential scanning calorimetry. All films dried quickly are composed of polymer in the left-handed α-helical form. All samples studied which have molecular weights above 2.3 × 104 are similar in crystallinity and the left-handed α-helices in them crystallize to ω-helices during slow evaporation. In the low molecular weight region, however, the left-handed α-helices reverse to right-handed α-helices during slow evaporation, and the right-handed α-helices, in turn, reverse and crystallize to highly ordered ω-helices upon heat treatment, although there is some simultaneous conversion to the β-form. The transition temperatures of the quick-dried films for conversion from the left-handed α-helix to the ω-helix and from the ω-helix to the β-form increase linearly with increasing molecular weight up to about 2 × 104, but no large molecular weight dependence is observed beyond that region.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2325-2331 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A torsional pendulum method was used to study the transient effects of sulfur dioxide at pressures up to 700 torr on the rigidity of Bisphenol-A polycarbonate at 25°C. Incremental increases in pressure led to a decrease and then to an increase in rigidity. Removal of sulfur dioxide at the rigidity minimum led to a rapid recovery in rigidity, but after apparent equilibrium had been reached the rigidity was not fully reversible. These observations provide evidence that sorption of sulfur dioxide results in structural reorganization of the polymer. A qualitative discussion of the data is presented.
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2391-2396 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Certain differences are pointed out between two recently published counting theorems for self-avoiding walks on a lattice.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2355-2361 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experiment is reported in which a simple laser light-scattering technique is used to measure the time for a critical turbidity to appear during the crystallization of polyethylene in xylene. The effect is examined over the entire range of solution concentration, and it is found that the relation between this concentration and temperature is linear for all solutions, provided that the time for turbidity to develop is arranged to be the same in all cases. In the appendix it is reasoned that similar results could have been obtained if, instead, times had been measured to a given degree of crystallinity rather than of turbidity. Departures from this linearity at low concentrations are taken as indicating multimolecular nucleation for all concentrations greater than about 1%.
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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2379-2390 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The band structure of an infinite linear polyaniline is investigated by using the HCO approximation. The degree of modelling of the limiting structure for the series by the linear oligomers so far synthesized is investigated. The upper bound of the wave-length of the long-wave ultraviolet absorption band for the limit is found, and the possibility of estimation of the conduction properties of its complex with iodine is indicated. The problem of replacement of the NH group in the chains by a more general group X is dealt with, and the dependence of the energy gap between the highest occupied and the lowest unoccupied band on the parameters of this group is determined.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2461-2473 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of a phenol-formaldehyde polymer with a deliberately introduced flaw were fractured in tension. The appearance of the fracture surface near the flaw suggested the disruption of particles pre-existing in the polymer. At a greater distance from the flaw, a featureless surface was observed which was succeeded by one showing interference colors. At still greater distances, linear features were observed to be lying in the direction of crack propagation which, in most areas, were regular and evenly spaced. There were indications that these features were formed by the curling of a surface film. The above observations are interpreted as providing evidence that tensile fracture is accompanied by plastic defórmation at the fracture surface.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2475-2488 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We examine several methods for analyzing the spectrum of light scattered from polydisperse polymer solutions. General expressions are reviewed for the inelastic scattering spectra and integrated intensities due to the pure translational normal mode of motion, using both heterodyne and homodyne detection, in terms of the molecular weights, concentrations, scattering form factors, and diffusion coefficients of the individual polymeric species, These results are used to obtain general expressions for the limiting slopes and intercepts of various rearranged versions of the equation I(v) = (A/π)2/(v2 + γ2) that permit linear plotting: I(v) is the intensity of light scattered at frequency v, A is the integrated intensity, and γ is the spectral halfwidth, K2D/2π, where K is the scattering vector and D the diffusion coefficient. These results are applied to the special case of a Schulz-Zimm distribution, neglecting form factors, to obtain explicit expressions relating the average diffusion coefficients determined by these procedures to other measurable quantities: the mean polymer radius; the diffusion coefficient of the weight-average species; and, together with the weight-average sedimentation coefficient, the weight-average molecular weight. Numerical calculations for two particular cases indicate the relative merits of the various data analysis procedures. Homodyne detection gives average values that are closer to weight averages than does heterodyne detection.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2051-2056 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Broad-line NMR spectra have been obtained at 90 MHz in the temperature region 140-530°K for four aromatic polyamides: poly(1,3-phenylene isophthalamide), poly(1,4-phenylene terephthalamide), poly(4,4,-diphenylene terephthalamide), and poly(4,4,-diphenylene isophthalamide). For the latter three materials, a broad-line narrowing process occurs in the 210-370°K region. At temperatures above 340°K a complex line shape is observed for all samples. Possible causes of these processes are discussed, and comparison made with dynamic mechanical results.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1853-1880 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the Green's function (GF) method of Lifshitz can be applied to conformational defects in polymers by taking correctly into account the actual geometrical configuration of the molecules. In contrast with methods currently in use in polymer dynamics, this method is not restricted to the calculation of the density of states, allows the treatment of infinitely long chains, and provides a direct assignment of typical frequencies to certain defect types. Furthermore, arbitrary frequency accuracy can be obtained with computer time drastically reduced from that required by other methods. A short review is given of the computation of experimental quantities which are related to phonons (in harmonic approximation, but in the presence of defects) and which can be obtained from the GF. Expressions are derived for the matrix elements of the harmonic GF of zigzag chains, valid for a general force field. The symmetry of the defects is taken advantages of by introducing symmetry coordinates.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1903-1915 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of an interferometric method for determining partial specific volumes of macromolecules is briefly reviewed. The experimental technique developed in this laboratory is described. Detailed results are given on the partial specific volume of ovalbumin in aqueous solution and its dependence on pH and KCl concentration. The results are compared, as far as possible, with dilatometric results obtained in another laboratory. The contribution of a change in partial specific volume of the macromolecules and in the partial specific volume of the water associated with them to the results is analyzed, and the scope of a possible complication due to changes in molecular polarizability is pointed out.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1941-1947 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behavior of Maxwell and of Wagner models with temperature-dependent elements is discussed. It is shown that these models can not be equivalent under nonisothermal conditions. It follows that the theory of equivalence of models does not apply to temperature-induced transients.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1949-1966 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization during polymerization of p-xylylene from the gas phase has been studied between 200 and -196°C. From room temperature to -17°C the polymer crystal morphology changes in that the crystallinity decreases. In this range the process is thought to be of the successive polymerization and crystallization type. The morphology is in agreement with this mechanism, of the folded-chain β-polymorph type with proper epitactic orientation of the chains with respect to the support surface. At -78°C an intermediate, poorly crystallized polymer results. At 196°C the reaction is most likely of the simultaneous polymerization and crystallization type. The morphology is, in agreement with the changed mechanism, of a metastable, irregularly folded β-polymorph type with no orientation of the chains relative to the support surface. No significant changes in molecular weight were observed in the polymers produced between 26 and -196°C.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1999-2007 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of crystallites in a bundle of parallel cotton fibers was studied by x-ray diffraction. The intensity distributions of the 101 and 002 diffraction rings showed the distributions of (101) and (002) planes to be identical within the limits of accuracy. Therefore, the crystallites in the cotton fibers very likely had random orientation about their long axes. The orientation distribution of these axes was calculated by using the intensity distribution of the 002 diffraction ring. The cylindrically symmetrical density distribution J(β) thus obtained was multiplied by sin β to obtain the distribution of relative numbers of crystallites at given angles β to the long axis of the fiber. The average 〈β〉 was found to be in agreement with the value of 〈sin2β〉 measured from the 002 diffraction ring. The intensity distributions on the 101 and 002 diffraction rings showed small fluctuations. These fluctuations appeared much stronger in the J(β) and sin β J(β) distributions, indicating clear discontinuities in the pitch angle distribution.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2231-2238 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-angle x-ray scattering methods have been applied to determine the parameters of the scattering materials in horn keratin. A low-angle camera of Kratky's latest design has been used for the experimental measurements. By treating the substance as a densely packed system, the evaluation of the parameters has been made after theories of Porod and Kratky. Pore analysis of the substance yields a specific inner surface of 4.7 × 10-1m2/cm3, a heterogeneity distance lc = 290.2Å and a reduced inhomogeneity length lr = 99.4Å. The volume of the pores has also been determined approximately.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2249-2257 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Peroxide radical concentrations were measured from both PET and nylon 6 fibers mechanically stretched in air at room temperature and quickly quenched into liquid nitrogen. The radical concentrations depend on degree of stretching as well as conditions under which the fibers were made, i.e., morphology. Drawn fibers of PET and nylon 6 produced peroxide radical concentrations of the same order of magnitude at the breaking points. These results indicate that chain scissions occur both in PET and nylon 6 under mechanical stretching.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2297-2300 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2073-2083 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conditions have been found for the etching of poly(ethylene terephthalate) with water so that the crystalline portions alone remain. Initial sample and hydrolysis products are analyzed by extraction of low molecular weight products; density, viscosity molecular weight, and endgroup determination; heating-rate-dependent thermal analysis; low-angle and wide-angle x-ray analysis; and electron microscopy. On hydrolysis of a 67% crystalline polymer at 180°C for about 300 min, almost fully crystalline extended-chain oligomers can be obtained with about 65% yield. The morphology of melt-crystallized poly(ethylene terephthalate) and the melting behavior of oligomer lamellae are discussed.
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2085-2092 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-crystallized poly(ethylene terephthalate) and etched oligomer lamellae from the same polymer have been annealed under vacuum at temperatures between 200 and 260°C and times between 3 and 48 hr. The annealed samples were analyzed through determination of viscosity-average molecular weight, x-ray low-angle spacing, density, heat of fusion, and variation of melting point with heating rate. In all cases it could be shown that the crystal lamellar surfaces remained chemically reactive. Chain folds and chain ends in the surface were converted by chemical reaction to tie molecules between different crystals or different locations on the same lamella.
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2101-2105 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2125-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The validity of Silberberg's hypothesis concerning the conformation of branched polypeptides was tested by studies on solutions and on monolayers. The poly(α-amino acids) investigated consisted of poly-L-lysine backbones with side chains of poly(gamma;-benzyl L-gutamate) and poly(β-benzyl L-aspartate). In solution, the conformation was studied in the mixed solvent chloroform-dichloroacetic acid. Optical rotatory dispersion measurements demonstrated the existence of a helix-coil transition which is a function of the length of the side chain. A significant “transition curve” appeared between 9 and 15 residues. From the results, it may be assumed that the poly-L-lysine backbone is extended in a coiled conformation and the side chains are coiled or helical, depending on the number of glutamate residues. At the air-water interface, a discontinuity in the surface-pressure curve appears between 9 and 15 residues per side chain. The similarity with the results obtained in solution appears significant; however, this has to be confirmed with methods more specific for structural modifications.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2155-2166 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A diffusion equation for the distribution of ionic impurities in a polymer under a dc field has been solved analytically for the conditions that neither injection nor absorption of impurity ions takes place at either electrode and that the ions do not interact. By using the solution of the diffusion equation, an ionic contribution to the complex dielectric constant is calculated. The most important results are as follows. (1) At high temperatures and low frequencies, the dielectric loss factor of the polymer decreases exponentially with the time elapsed after the application of the dc bias. (2) The dielectric constant is not greatly affected by the bias. (3) The ionic contribution to the loss factor in the absence of the dc bias is represented as ∊i″ = 4πνDq2/ωkT, where ν is the density of mobile ions, D the diffusion coefficient, q the charge of an ion, ω the angular frequency, k the Boltzmann constant, and T the absolute temperature. (4) A method is presented for distinguishing between the apparent activation energy for diffusion and that for generation of mobile ions.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2173-2187 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Factors which affect and broaden molecular weight distributions are investigated for polymerizations in catalyst particles which are accumulating polymer, such as Ziegler polymerizations of olefins. Expressions for the Q value, or ratio of weight-average to number-average molecular weight, are derived for simple, but important linear models. These expressions are of the form Q = FSX for a kinetic scheme in which polymer chains have an infinite growing lifetime, and Q = 2FGSX for a kinetic scheme in which termination by hydrogen is dominant and each site produces many chains. The factors F, G, S, and X are equal to or greater than unity: F depends on particle geometry and the nature of diffusion and reaction; G depends on environmental history of the particle; S depends on the distribution of site activities; and X depends on the distribution of particle sizes. Effects of reactor type are also studied quantitatively.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2223-2229 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Specific heats of a series of plasticized and unplasticized poly(vinyl chloride) compositions have been determined by a differential scanning calorimeter over the temperature range 200-400°K. The glass temperatures were higher and the specific heat values at 300°K lower with phthalate esters then with esters of aliphatic acids; those values were also higher and lower, respectively, with benzyl-containing esters than with the methyl or octyl esters. The data were treated by a computer technique and plotted. A mathematical expression was developed which would describe the curves obtained when specific heat was plotted against temperature, and provided values in each case for the glass temperature and the specific heat at the glass temperature and at 300°K, as well as other descriptive parameters.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2437-2452 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on an analogy with the growth of kink bands in oriented and annealed crystalline polymers, a mechanism is suggested for the deformation-induced spherulite-to-fibril transformation. Oriented and annealed material was employed as a model because it has roughly the same structure as the lamellar bundle of the spherulite. Under conditions that minimize the fibrillar quality and maximize the lamellar bundle quality, oriented and annealed crystalline polymers deform with the formation and growth of kink bands. The characteristics of kink bands are the sharpness of the kinks, occurring within zones ca. 100 Å wide, and mirror symmetry of the fibrils about the kink-zone planes. The spherulite-fibril transformation is suggested by analogy, then, to occur in the narrow zones that indeed are often found and to result in mirror symmetry of the chain axes about the transformation-zone planes, which may not exactly occur because of a tendency for the tie molecules to be pulled from the lamellae during drawing. The implications for the transformation are (a) that the microfibril backbones are derived from the tie molecules between lamellae and (b) though some unfolding occurs as blocks that were adjacent within the lamellae become separated, the crystals remain mostly intact during the transformation. The analog is supported by or at least is consistent with various other results, including those from morphological and small- and wide-angle x-ray studies.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2453-2459 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Rayleigh linewidth Γ of light scattered by dilute aqueous solutions of polystyrene latex spheres has been measured by using time-dependent photocurrent signal correlation with a precision typically of 0.5-1% over a range of scattering angles θ. With independent measurements of the diffusion coefficient D from D = lim K → 0 (Γ/K2), the diameter of the sphere d by means of electron microscopy, and the hydrodynamic shear viscosity η, we have confirmed the Stokes-Einstein relation D = kT/3πηd to within 1% if we take into account the effect of polydispersity on our Rayleigh linewidth data. We also find that dEM = 907 ± 56 Å for sample LS-1132-B as reported by the Dow Chemical Company differs from our dSB = 847 (±1.6%) Å ≈ dEM = 851 (±2%) by about 7%, which is outside the limits of error of our experiments. The subscripts EM and SB denote electron microscope and self-beating, respectively, while K ≡ (4π/λ)sin(θ/2) is the magnitude of the momentum transfer vector.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1505-1507 
    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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  • 189
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model relating crystal orientation in a semicrystalline polymer to the deformation of polymer spherulites is proposed. The distribution function for orientation of crystallites within crystal lamellae is assumed to be a function of lamellar orientation. In addition to the orientation of crystal lamellae in affine fashion, several parameters are introduced to characterize the untwisting of the crystal lamellae and the four different types of orientations of the crystallites within the crystal lamellae in the undeformed and deformed states of the spherulite. The model was tested by experiments in uniaxial stretching of a low-density polyethylene. The theoretical distributions of orientation of given reciprocal lattice vectors of the crystallites, such as the reciprocal lattice vectors of the (110) and (200) crystal planes, are compared with the results of x-ray diffraction experiments. It was found that the most important factors in fitting the model to experimental results are: (a) the fraction of crystallites having random orientation within lamella and, in turn, representing the degree of imperfection of the lamella in the undeformed state; (b) the ease of transition of crystal orientation within lamella from b-axis orientation parallel to the lamellar axis to two types of c-axis orientations (type Ca and type Cr) parallel to the stretching direction; and (c) the fraction of crystallites having orientation in type Cr (unfolding mechanism) rather than type Ca (rotation mechanism).
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1881-1901 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An exact method is presented for calculating the density of states and any complex matrix element of the harmonic phonon Green's function of single polymer chains of infinite length. The method takes advantage of the one dimensionality of the Brillouin zone. In comparison to the standard root sampling method, the method presented here has all the advantages of a fully analytic procedure (in particular, smooth curves instead of histograms) and offers and enormous increase in accuracy while at the same time drastically decreasing the computer time. For illustrational purposes, the method is applied to the defect model of Opaskar and Krimm and to the diatomic linear chain. In addition to the reproduction of the results obtained by Opaskar and Krimm, explicit expressions for the resonance and localized modes are derived.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1917-1930 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical description of the ductile transition of glassy polymers in tensile creep is given. It predicts the delay time for plastic yield as a function of stress. The model assumes first-order rate expressions for the rate of change of loadbearing elements. The rate constants are given by a modification of the absolute reaction rate concepts of Eyring, where the energy barrier for breakdown of the bonding elements is asymmetric. This leads to an equation for the yield delay time as a function of the height of the energy barrier in the unstressed state, an activation volume, and a critical stress required to overcome the initial barrier asymmetry. The model has been compared to creep delay time experiments on polysulfone, polycarbonate, and poly(methyl methacrylate). It is able to predict the stress dependence for the onset of ductility in these materials with greater accuracy than previously reported equations.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2343-2354 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Counterion activity coefficients in solutions of dextran sulfate with and without added salts were determined potentiometrically by using a cation-exchange membrane and a sodium glass electrode. Dextran sulfate was shown to interact with monovalent cations in the order of preference: K+ 〉 Cs+ 〉 Na+ 〉 Li+, whereas no specificity was found for bivalent cations. On the basis of light-scattering measurements, the expansion of the dextran sulfate polyion in solutions of alkali metal salts was found to fall in the same order as the counterion activity coefficients in salt-free solutions. It was also shown that the dextran sulfate polyion assumes a more extended conformation in magnesium chloride solution than in calcium chloride. These results were substantiated by measurements of solution viscosities.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2409-2421 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A description is given of an apparatus for the continuous recording during crystallization of the spherulite radius, in the range of one half micron to a few microns, by scanning the Hv scattering pattern. At the same time the apparatus measures the change in intensity of the transmitted depolarized light, which is a measure of the overall rate of crystallization. The theoretical aspects of this measuring procedure are briefly discussed on the basis of light scattering by perfect and imperfect spherulites.
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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2397-2407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene single crystals deformed on copper and NaCl single-crystal substrates by the method of Gleiter and Argon were examined in transmission electron microscopy attached to carbon film carriers constraining them to their deformed state and also after they have been removed from the deformed substrates and were allowed to relax. It was observed that the imposed shear strains can be accommodated by the polyethylene crystals by a combination of debonding from the substrate, elastic flexing, extensive inplane twinning and martensitic shear transformations, buckling, and tearing. No contrast effects suggestive of slip lines could be observed in dark field studies, and the gold droplet decoration technique failed to detect any unambiguous slip lines. From this it is concluded that the critical shear stress for slip is always higher than that for twinning and martensitic shear transformations, and that crystals will deform preferentially by these latter modes.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2189-2208 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain-backbone motion in glassy polycarbonate has been investigated both under isothermal stress, and also under zero stress during isothermal annealing of freely contracting film specimens. In both types of experiment, backbone motion was detected by measuring the change in infrared dichroism. The dichroism of absorption bands at 1364 and 2971 cm-1, which have transition moment vectors directly related to the chain-backbone orientation, was studied. Under tensile stress in the homogeneous region of deformation, changes of up to 2.2° in the mean chain-backbone orientation angle were measured at 23°C. With the onset of cold drawing a total orientation change of some 8° was observed. For the isothermal annealing experiments, a film specimen holder employing conductive heating with radiative losses was employed. It enables infrared measurements to be made while the temperature of the contracting specimen is maintained constant to ± 0.5°C. Oriented specimens were prepared by isothermal stretching of polycarbonate films to strains of the order of 100%. Changes in the mean chain-backbone orientation angle were observed during annealing of these oriented films at temperatures between 80°C and the glass transition (149°C). Chain motion proceeded during annealing, and chain segments were observed to move cooperatively. The temperature at which the polymer is prestretched has a pronounced effect on its subsequent relaxation during annealing: when the sample was stretched at 23°C. motions were detected during annealing at temperatures as low as 81°C, while, if it was stretched at 154°C, no motion was detected at annealing temperatures below 127°C. The data are discussed in comparison with theories of the glassy state that predict the absence of chain-backbone motion at temperatures significantly below the glass transition. A shift in frequency of the νa (CH3) absorption peak in stretched polycarbonate was measured by using polarized radiation. The effect was interpreted in terms of changes in the intermolecular bonding structure of the oriented polymer.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2239-2248 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow curves of fractionated polydimethylsiloxanes of different molecular weights were obtained over a wide range of shear rates, from 3 × 10-1 to 4.3 × 106 sec-1, by use of a gas-driven capillary viscometer designed to decrease the experimental error in high shear rate region. Non-Newtonian flow can occur at molecular weights below the critical molecular weight Mc for the entanglement of polymer chain. The critical molecular weight M′c for the onset of the non-Newtonian flow is identical with that of the segment of viscous flow. For the polymer of molecular weights from M′c to Mc, the upper Newtonian viscosity increases with an increase in molecular weight. Above Mc, the upper Newtonian viscosity is almost independent of the molecular weight.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2259-2280 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photocurrents induced by ultraviolet illumination of poly(ethylene terephthalate) (Mylar) and polyethylene specimens supplied with aluminum electrodes in a sandwich configuration have been studied in the wavelength range 380-180 nm. A description is given of the precautions taken to ensure that artefacts such as photoelectric emission external to the specimen do not influence the measurements. In both materials, a fast and a slow transient are present. Measurements on polyethylene show that the magnitude of the response is linearly dependent on the light intensity and is essentially thickness independent. This behavior leads to difficulties in interpretation in terms of known conduction processes. In Mylar it is shown that hole injection from the positive electrode into the polymer is responsible for the observed currents, and evidence to associate a similar process with the effects in polyethylene is presented.
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  • 198
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A versatile double-beam polarization fluorimeter has been constructed for measuring the polarization of fluorescence from polymer solutions, melts, and glasses. Polarizations can be determined over a range of temperatures from -20 to +80°C in a controlled atmosphere with a precision of ±0.001 to ±0.005 for the studies reported herein. Data collected at different temperatures for 1.5 × 10-5M solutions of 9,10-diphenylanthracene (PA) in di-n-butyl phthalate (BP) fit a relation of the Perrin type, 1/P = (1/P0) + (ST/η1), where P is the polarization, T is the absolute temperature, and η1 is the solvent viscosity. The constants P0 and S were 0.400 ± 0.005 and (7.4 ± 0.3) × 10-3 P/°K, respectively. Polarizations were also determined at 25.0 ± 0.1°C for BP solutions containing 1.5 × 10-5M PA and polystyrenes at various weight fractions w2 and molecular weights M. Rotational friction coefficients ζr deduced from these data showed no dependence on M from 5.1 × 104 to 8.6 × 105 g/mole, and a gradual increase as w2 was varied from 0 to 0.1. It is concluded from these results that PA is an especially attractive emitter for rotational diffusion studies in nonaqueous systems, and that the abrupt changes in ζr with w2 and M observed for some other emitter-polymer systems and attributed to onset of coil overlap are not universal characteristics of such systems.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2305-2309 
    ISSN: 0098-1273
    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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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2313-2324 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Examination of longitudinal, cross, and skew sections of extruded polycaprolactam filaments with the polarizing light microscope reveal morphological features not previously described. In cross-sectional view, three distinct layers enclose a “homogeneous” central matrix. The outermost layer is characterized by large, birefringent, truncated cones extending upward from the surface. Associated with the cones and an entity in its own right is what appears to be a second layer of ultrafibrils. Below the latter is a fine-structured layer of submicroscopic spherulites. A combination of the above features forms the transcrystalline region of stressed melts. Row nucleation is evident on the surface of the filaments.
    Additional Material: 8 Ill.
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