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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1-16 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Approximations in the Avrami treatment of impingement which arise when the growing crystalline bodies are rods or disks are discussed, with particular reference to the single-crystal model. This model, previously fitted to the isolated primary crystallization of polymethylene, is extended to discuss the growth of the composite lamellar structures, axialites, and spherulites, and is here fitted to the crystallization of poly(ethylene oxide) and polystyrene. Both polymers are found to yield anomalous values of the Avrami exponent when analyzed in terms of the conventional Avrami equation. The new analysis reveals similarities in the behavior of all three polymers. The residual deviations remaining after the fit of the model to polymethylene and poly(ethylene oxide) follow the same pattern, and the temperature dependence of the rate constants associated with the model is similar for all three polymers.
    Additional Material: 5 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 17-24 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Of nine glassy polymers so far investigated, eight yield evidence that fracture propagation involves the formation and breaking of craze material. All eight produce fracture surfaces exhibiting interference colors to one extent or another and even the colorless areas cause low angle x-ray scattering. Ranked in terms of decreasing ease of colored surface formation, these polymers are poly(methyl methacrylate), poly(ethyl methacrylate), polystyrene, acrylonitrile - styrene copolymer, poly-α-methylstyrene, poly(vinyl acetate), a polyhydroxy ether, and polycarbonate. Only rigid poly(vinyl chloride) has failed to show evidence of precrack craze formation.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of ethylene with vinyl acetate, vinyl alcohol, and butene-1 have been investigated by differential thermal analysis. The method of fast heating is used to approximate a zero entropy production heating path. The activity of crystallizable units in the melt, the crystallinity, and the a-axis spacings are determined and compared with previous results for copolymers of ethylene and propylene and carbon monoxide. Carbonyl and hydroxyl groups form point defects, forming solutions in both the crystalline and amorphous regions. Methyl, ethyl, and acetate groups form large amorphous defects. The maximum melting point of polyethylene is calculated to be 142.6°C.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 41-52 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic moduli, E′ dyn, and loss tangents, tan δ, of polydimethylsiloxane and polydimethyldiphenylsiloxane polymers have been investigated by an in situ technique during γ-irradiation. These viscoelastic properties were calculated and plotted as a function of irradiation exposure time by measuring the free end displacements and resonance frequencies of polymeric cantilever reeds. The reeds were swept through a small frequency range from about 20 to 100 cycles/sec. The moles of effectively elastic chains per unit volume (v) of the two unfilled polysiloxahes were calculated from in situ modulus data and compared to values obtained utilizing the swelling technique. The approximate molecular weights between entanglements, Me, of these unfilled polymers were determined by extrapolation of moduli data to zero radiation exposure. The addition of a large silica filler, SiO2, into the polymers did not alter the crosslinking rates, and the filler did not enter into polymer - filler bonding.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 63-88 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory of tensile strength, based on the observation of cracks in specimens strained to breaking, is formulated. The treatment involves the assumption that a crack grows to a critical size by a nucleation process. When this critical size is exceeded the crack becomes unstable and propagates spontaneously to produce rupture. By comparing the predicted and measured strength, one can estimate the magnitude of the stress concentration factor in fibers. An interpretative analysis of experimental data obtained at various strain rates indicates that the resulting changes in tensile strength are due primarily to the changes in modulus.
    Additional Material: 13 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 527-528 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 532-534 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 529-531 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 535-537 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 538-542 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 571-586 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes in x-ray orientation brought about by the treatment of cotton and ramie with caustic soda of different concentrations have been studied. With ramie the effect of the treatment is to decrease the x-ray orientation, while with cotton the reverse is true. The cause of this difference is traced to a difference in the morphology of the two fibers rather than a difference in their fine structure.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 545-557 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two sets of dynamic mechanical property data and some stress relaxation data for semicrystalline, linear polyethylene are treated by data reduction methods previously described. These data can be represented by a master plot of reduced modulus versus reduced frequency and two sets of temperature-dependent shift factors. The first of these factors reflects the change of viscoelastic relaxation times with temperature. The second represents a separable change of modulus with temperature which applies over the entire time or frequency range of the experiments. This change is larger and in the opposite direction to that found applicable in the behavior of noncrystalline plastics and rubbers. The two sets of dynamic data show the same frequency-temperature dependence which can be represented by an activation energy of 22 kcal./mole. Small differences in the modulus-temperature dependence are attributed to differences in molecular weight or annealing conditions. The stress relaxation data superposes to a curve in good agreement with the dynamic data but with a factor of 20 difference in time scale. This difference is attributed to the finite strains used in the stress relaxation measurements. Such strains might be expected to increase free volume in simple extension deformations and so accelerate the relaxation.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 559-569 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of poly-4-methylpentene-1 have been measured in torsion in the temperature range from 25 to 160°C. at frequencies from 10-3 to 10 cps. Two transitions are found. The first, with a peak at 40°C. at 1 cps, appears as a normal glass transition. A broad high temperature peak appears at 130°C. The dynamic compliance-frequency data can be superposed by the conventional method of reduced variables for temperatures up to 100°C. The temperature dependence of the shift factors follows the WLF equation. Above this temperature, superposition can be achieved by applying horizontal and vertical shifts to both components of the dynamic compliance. When the vertical shift is permitted, the range of applicability of the WLF equation is extended to 160°C.
    Additional Material: 6 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 587-598 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NMR measurements on undrawn polyethylene (PE) samples in contact with a solvent such as C2Cl4 indicate an increase in the mobility of the mobile chain segments as compared to dry samples. Highly drawn PE shows no such effect. This is because Sa, the sorption per unit mass of noncrystalline material present, decreases from 20.9 wt.-% (dry basis), found for undrawn quenched PE, to 0.63 wt.-% after drawing (Sa determined at 25°C. and 0.80 vapor activity). Drawing also reduces the segment mobility according to the NMR spectrum. It is shown that these effects are caused by considerable structural changes occurring in the noncrystalline regions of PE upon drawing. Annealing of drawn PE samples at successively higher temperatures leads to a gradual relaxation of the noncrystalline regions towards the state characteristic of undrawn PE. With increasing annealing temperature Sa as well as the mobility approach values found with undrawn PE.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 869-880 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The configurational entropy of the polyethylene chain at the melting points calculated in two ways. In both calculations, tetrahedral angles and discrete trans and gauche arrangements of all bonds are assumed, and trans bonds are assumed more stable than gauche by energy U1. First, calculations are made on chains of up to N = 18 bonds, disallowing all configurations having overlapping atoms, and the result is extrapolated to large N. Second, a calculation is made directly for long chains, with overlaps excluded only over every short chain segment. The results are in almost exact agreement, suggesting that the second method can be safely used with other molecules. The calculated configurational entropy is in line with that suggested by the entropy of fusion, assuming the chains to acquire a configurational freedom in the melt which approaches that of independent chains.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 881-897 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The angular distribution function P(θ) for intensity of light scattered by a dilute solution of comblike branched molecules has been determined for three situations of some interest for evaluation of experimental data: (1) the molecules are identical with branches of equal length attached equidistantly along linear backbone chains; (2) the molecules are homogeneous in mass, with the same number of branches on each molecule, but the branches are distributed at random along the chain; (3) branches and main chains are still uniform, but the molecules are heterogeneous in mass with the number of branches per molecule distributed according to the binomial distribution and the branches in any molecule spaced randomly along the backbone. Examination of numerical results shows that the scattering functions for models (1) and (2) are not very different. The function for case (3) is somewhat different from the others when the mean number of branches per molecule is small but they contain a large fraction of the mass of the molecule. Over a limited range of the pertinent variables (corresponding roughly to observations on typical vinyl polymers of molecular weights up to 106) all three functions agree quite well with P(θ) for homogeneous linear chains with the same mean-square radius of gyration.
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  • 17
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of the α polymorph of nylon 4 has been determined from the x-ray diffraction patterns of uniaxially oriented monofilaments. In general the crystal structure of α nylon 4 is similar to that of α nylon 6. The unit cell is monoclinic with the following dimensions: a = 9.29 ± 0.05 A., b = 12.24 ± 0.05 A., c = 7.97 ± 0.05 A., and β = 114.5 ± 1.0°. There are eight monomeric units in the unit cell. The theoretical density is 1.37 g./cc. and the observed density 1.25 g./cc. The space group is P21. The nylon 4 chains are of the extended planar zigzag type, with the plane of the zigzag approximately parallel to the a axis of the unit cell. Along the a axis, every other chain is inverted - an antiparallel arrangement of chains - thus permitting complete hydrogen bonding and the formation of sheets of nylon 4 chains. Along the c axis of the unit cell, the second sheet is displaced by3/10 of the b axis, thus leading to a staggered arrangement of sheets. The sheets are held in place by van der Waals forces.
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  • 18
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In addition to the α polymorph, two crystalline forms of nylon 4, the β and δ polymorphs, have been observed and studied.The β polymorph of nylon 4, which has not been found in a pure condition, appears to be similar to the β polymorph of nylon 6. The extended planar zigzag conformation of chains, found in the α polymorph, is present also in the β polymorph. Three models have been proposed to explain the observed data. In model 1, the staggered shear of van der Waals bonded sheets found in the α polymorph is abandoned; in model 2, the sheets are displaced by 1/2 the b axis, and in model 3 the chains are arranged in a parallel array. The β polymorph is converted to the α form in air upon heating for 11 min. at 227°C. and upon immersion in water for 2 hr. Models 1 and 2 would be converted to the α polymorph by a slippage of the van der Waals bonded sheets while the conversion from model 3 would involve a rupture of hydrogen bonds, a rotation of the chains through 90°, and the reformation of hydrogen bonds. The δ polymorph is formed by rapidly quenching extruded nylon 4 against chilled rolls. It is a metastable form which has only been observed in an unoriented condition. Upon orientation it is completely converted to the α polymorph. In addition to this, its conversion to the α form occurs under conditions similar to the β-α transition. The observed diffraction pattern can be indexed on the basis of a hexagonal packing of chains. High-temperature x-ray diffraction studies of the α polymorph suggest that the δ form, or a structure similar to it, is the high-temperature form of nylon 4.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 975-996 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Random copolymers of N-n-butyl-, N-n-octyl-, or N-n-octadecylacrylamide with acrylonitrile were prepared in tert-butanol at 60°C. to test the effect of amide homologs as internal plasticizers. At room temperature under high deformations all samples showed brittle failure; at 100°C. flexible and resilient copolymers were obtained. At low deformations, torsional stiffness values Tf followed the equations of Wood, Fox, and Dimarzio and Gibbs, the latter two modified by use of mole fraction instead of weight fraction. Mole fraction appeared to function better than weight fraction for these special cases where wi 〉 2mi and where modulus-temperature curves were broad. Because literature values for the glass (or brittle) temperatures of homologs of poly-n-alkyl acrylates, methacrylates, n-alkyl styrenes and alkenes, and estimated values for poly-N-n-alkylacrylamides, plotted as a function of the logarithm of the number of single bonds in repeat units, extrapolate to an average value of -111°C. at a chain length of eighteen carbon atoms, and because side-chain melting points of linear eighteen carbon side-chain homologs appear to have a common value of 48-50°C. regardless of structure, it was concluded that similar glass and melting transitions are obtained when the side chain reaches eighteen carbon atoms in any series of homologs. Transitions for longer side-chain lengths then approach the limit of a polyethylene graft, where Tg is -81°C. and Tm is 137°C.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 101-111 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The performance of the gel permeation chromatography (GPC) technique was studied with several commercial samples of linear high density polyethylene. A comparison of these data was made with those obtained from the elution column technique based on fractional dissolution. GPC gave reproducible fractionation data in the molecular weight range of 103-106. These data were obtained from two columns in series with nominal capacity of 1-104 and 1-106A. Polyethylene fractions of known molecular weights are required as calibration standards and for many commercial polyethylenes it is necessary to increase sensitivity at molecular weight higher than 106.
    Additional Material: 8 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 327-347 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amorphous films of Lexan polycarbonate have been exposed to acetone vapor at controlled temperatures and partial pressures in order to study sorption kinetics and thermodynamics and polymer crystallization behavior. Sorption isotherms show a discontinuity is slope at or near the depressed glass transition, which itself was identified by torsion pendulum measurements. Crystallization abruptly begins to occur at partial pressures equal to or slightly above that of the solubility transition and is manifested by delayed desorption and whitening phenomena. In this process 20% crystallinity is usually developed, as measured by calorimetry which, however, produces a 40% drop in acetone solubility. Although the depressed glass temperature is near 0°C. in saturated atmospheres - a drop of 145°C. - the melting point is only depressed 60 or 70°C. Such disparity probably accounts for the enhanced polycarbonate crystallization rate in acetone over that in the dry bulk polymer above the normal Tg.
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  • 22
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 349-358 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Observation of optical interference fringes at the tip of a crack in a glassy polymer allows the construction of the configurations of the crack tip and the craze that precedes it. The craze extends 25 μ beyond the crack tip in poly(methyl methacrylate) and 550 μ beyond the tip in the polystyrene studied. The craze at the crack tip in PMMA may be seen to deform elastically as much as 100% under stress before crack propagation recommences. Such deformation is estimated to account for as much as 40% of the nominal Griffith energy of crack propagation.
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  • 23
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 365-374 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of polystyrene and poly(methyl methacrylate) have been prepared by bulk polymerization under conditions previously investigated in the literature. The molecular weight distributions were determined for early-conversion samples by gel permeation chromatography, and the experimental distribution curves were compared with calculated curves based on kinetic data. The agreement between the experimental and calculated curves was such as to indicate the utility of gel permeation chromatography in the investigation of polymer reaction kinetics and mechanisms.
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  • 24
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 375-384 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-temperature internal motions of the following polyesters have been investigated by broad line nuclear magnetic resonance: poly(methylene terephthalates) (2-6 methylene groups), poly[1,4-(dimethylene)cyclohexylene terephthalate], poly(diethyleneglycol terephthalate), poly(1,2-propylene terephthalate), poly(1,4-phenylene terephthalate), poly(2,2,3,3,4,4-hexafluoropentamethylene terephthalate), poly[1,4-phenylenebis(dimethyl) siloxane], and poly(2,6-dimethylphenylene oxide). No complex line structure was found for any of the samples. Molecular motions in the polyesters appear to be restricted by polar forces arising from the ester groups. Above - 196°C. the line width decreases smoothly with increasing temperatures for all polymers except poly[1,4-(dimethylene)cyclohexylene terephthalate] and poly[1,4-phenylenebis(dimethyl)siloxane]. These two show a definite transition in line width at -20°C. and +12°C., respectively, caused by the onset of considerable internal motion. At -196°C. the lattices are rigid except for polymers containing methyl groups: poly(1,2-propylene terephthalate), poly[1,4-phenylenebis(dimethyl) siloxane], and poly(2,6-dimethylphenylene oxide). Internal motion that can be ascribed to be a reorientation of the methyl groups is present at -196°C. for these three polymers, as is demonstrated by comparison of experimental second moments and those calculated on the basis of various models.
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  • 25
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 447-464 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements are described of the rates of crystallization and crystal melting temperatures in stretched test pieces of trans-polyisoprene, crosslinked to various degrees. The increase in rate with extension are attributed to the corresponding increases in melting temperature and hence degree of supercooling. The rise in the melting temperature of both the α- and β-crystal forms is found to be in satisfactory agreement with Flory's treatment of oriented crystallization. The changes in tensile stress are also generally in accord with the formation of oriented crystallites. For the more lightly crosslinked materials, a pronounced rise in tensile stress occurred during the later stages of crystallization, at extensions below about 100%. Reasons are given for attributing this phenomenon primarily to the relatively large contraction in volume on crystallization, rather than to the formation of folded-chain crystallites.
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  • 26
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 437-446 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering and viscosity have been measured at 25°C. for dilute solutions of six unfractionated polyoxymethylene samples in the mixed solvent hexafluoroacetone-water (mole ratio 1/1.7) slightly buffered with triethylamine. Dialysis equilibrium through porous Vycor glass thimbles indicates that the polymer is strongly solvated by the hydrate (CF3)2C(OH)2, and this must be taken into account in evaluating weight-average molecular weights from the light-scattering data. Over the molecular weight range 23,000-185,000, the intrinsic viscosities (in deciliter per gram) follow the relation \documentclass{article}\pagestyle{empty}\begin{document}$ [\eta] = 8.7{\rm} \times {\rm}10^{ - 4} M_\upsilon ^{0.69} $\end{document} The corresponding unperturbed dimensions are σ = 2.3 ± 0.2 or r02/nl2 = 10.5 ± 1.5.
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  • 27
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 227-242 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polypropylene was oxidized with nitric acid in a manner contrived to remove its amorphous component. Concurrent with the loss in weight there was an increase in crystallinity, a decrease in molecular weight, a drop in melting point, and a change in visible structure. The crystalline component, which survived from polymer which had orginally crystallized isothermally, consisted of separated spherulites. These spherulites could be broken apart into lamellae which gave electron diffraction patterns like those now associated with a variety of solution-grown single crystals. As opposed to the high molecular weight of the unoxidized parents, the lamellae which survived the acid treatment consisted of short chains whose length depended on the temperature at which the parents had crystallized. If, as diffraction studies indicate, these short molecules are lined up in rank and file, then the length of the molecules and the height of the lamellae should correspond. The heights of the lamellae could not be measured precisely enough to establish an exact correlation, but the variations in average chain length calculated from viscosity data at least approximated the heights of the lamellae which were observed visually.
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  • 28
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 267-281 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intercrystalline links in polyethylene have been revealed by crystallizing from the melt mixtures of fractionated polymer and the linear hydrocarbon n-C32H66, the latter constituent being removed later by washing at room temperature in an organic solvent. These fibrous links measure up to 15,000 A. in length and are 30-300 A. in thickness. Molecular chains are oriented parallel to the lengths of the links, and apparently nucleate on tie molecules formed by the simultaneous crystallization of different parts of the same molecule on the surfaces of different, and often widely separated, crystals. The maximum length of the links found in a given polymer varies as the square root of molecular weight, and there are indications that molecules in the melt are much more extended than is predicted by conventional configurational statistics. The links are under tension and presumably exert a significant influence on physical properties.
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  • 29
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 289-298 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Uniaxial deformation of polyethylene single crystals has been reported in the previous papers of this series. This paper presents an extension of this study to the simultaneous biaxial deformation of polyethylene single crystals. Diamond-shaped crystals containing {110} fold domains and truncated crystals containing in addition {100} domains were used in these experiments. The results show that these crystals fail at deformations as low as 6%, giving rise to cracks predominantly in the a direction. Electron diffraction patterns suggest that {310} twinning is more favorable than {110} twinning at the lower degrees of deformation. No phase change from orthorhombic to monoclinic unit cell is observed.
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  • 30
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 491-500 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations previously developed for the light scattering of polar chain polymers subjected to orientation by an electrical field are extended to the case where the elementary dipoles have arbitrary direction with respect to the chain contour. As an illustration of the theory, measurements were made of the light scattering of nitrocellulose solutions as a function of the angle of observation, the field strength, the direction of the field, and the frequency of the field. The principal results obtained were: the molecules are deformed by the electrical field; orientation is due primarily to a permanent electric moment whose component per chain segment is of the order of 4 Debye; and the relaxation times for molecular orientation are of the order of magnitude predicted by the theory of Stockmayer and Baur.
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  • 31
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 501-505 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NMR linewidth studies of nylon 66 as a function of temperature and applied tensile stress have been conducted. The principal motional transition temperature was found to be shifted to higher temperatures with stress application by 9°C./g./den. At any given temperature, increased stress resulted in an increased linewidth. An attempt was made to correlate the shift in the motional transition temperature with the concept that a segment experiencing motion must do work against the applied tensile stress.
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  • 32
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 475-489 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction, sonic velocity, and birefringence measurements were used to study the variation of the apparent melting point of strained natural rubber and polychloroprene vulcanizates with elongation ratio and crystallization temperature. The procedure of Hoffman and Weeks was employed to obtain the thermodynamic melting point, tm, for each elongation ratio α. The parameter β relating to the distribution of fold lengths is unusually large for low elongation ratios and decreases into the usual range only at higher elongations. The observed variations of tm with α for these two polymers are compared with the theoretical predictions of Flory and Roe and Krigbaum. Although the predictions of the Flory theory depend somewhat upon the value assigned for the number of repeating units per statistical link, and this parameter is not well known for polychloroprene, we nevertheless conclude that his treatment offers a better representation of the melting point elevation for high elongations. Due to the approximations introduced, the treatment of Flory is not valid for lower elongations. Any attempt to improve this treatment must begin by specifying the free energy of the semicrystalline system, which implies a knowledge of the distribution of crystallite orientations and how this distribution varies with strain and with the crystallization conditions.
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  • 33
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase equilibria between linear polyethylene and a number of organic diluents of varying type have been investigated. The diluents include aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and ketones. It is found that n-octyl alcohol, n-decyl alcohol, n-lauryl alcohol, p-tert-amyl alcohol, p-octyl phenol, p-nonyl, phenol, diphenyl, diphenylmethane, diphenyl ether, benzyl phenyl ether, and anisole are Θ-solvents for linear polyethylene at temperatures between 120 and 200°C. Thermodynamic interactions are discussed in relation to the type of diluent.
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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 519-520 
    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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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 521-522 
    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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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 523-526 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 959-974 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of poly(m-xylylene adipamide) was reinvestigated by x-ray diffraction. It is found that the helical chain model proposed by Yoda et al. needs to be corrected to a large extent. The unit cell obtained is triclinic with dimensions a = 12.01 A., b = 4.83 A., c = 29.8 A. (fiber axis), α = 75.0° = 26.0°, and γ = 65.0°, in which one molecular chain with two chemical repeating units is involved. The space group is C1i-P1. An almost planar zigzag chain conformation with a small degree of contraction from the original planar arrangement is given. The CH2 planar zigzag chain and the aromatic rings are so oriented that their planes are inclined to the c axis at an angle of a few degrees. The hydrogen-bonded sheets nearly coincide with the (100) plane and the aromatic rings are close to the (120) plane, which is nearly perpendicular to the direction of hydrogen bonding.
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  • 38
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1009-1010 
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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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  • 39
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1011-1012 
    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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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 997-1008 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transformations of the polymorphic forms of polybutene-1 (I,II,III) were studied by infrared spectroscopy. Attenuated total reflectance spectra demonstrate that the II → I transformation occurs initially and most rapidly on the film surfaces. Electron irradiation experiments showed the II → I conversion can be suppressed by irradiation. The degree of suppression was dependent on the irradiation dose. Comparison of spectra on irradiation in air and vacuum indicate that radiation-produced radicals are scavenged by oxygen, preventing intermolecular crosslinking and allowing normal expansion of the helix during transformation. In addition, remolding an irradiated sample of II caused immediate conversion to I rather than its return to II as was noted when unirradiated samples are remolded. These observations are related to certain conformational changes in the molecular structure.
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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1022-1024 
    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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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), 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 effect of birefringence on the intensity of polarized scattered light from an oriented polymer film is analyzed on the basis of a model in which the scattering element is imbedded in a homogeneous birefringent matrix. The scattering intensity is shown to depend upon the polarizer and analyzer angles, the scattering angles, the sample birefringence and thickness, and the scattering coefficients for the four polarization combinations. Computer calculations for reasonable values of these parameters indicate that these corrections can be quite appreciable.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 243-265 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preliminary study of the isothermal crystallization of “even-even” polyamides reveals striking similarities in spherulitic morphology. The observed variations in textural features of spherulites of nylon 210, nylon 66, nylon 610, and nylon 1010 show parallel changes during growth conditions and conform to a definite sequence of behavior. At least four different types of spherulites exist in each polymer. Optical and x-ray techniques were used to examine some of these spherulites. Crystalline platelets possessing single-crystal properties have been grown in thin films of these polymers near their respective melting points.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 283-288 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 8 Ill.
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  • 45
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 599-610 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described for the conversion of polystyrene to poly(styrenesulfonic acid) without change in the molecular weight distribution; the reaction is performed at room temperature in 100% H2SO4 and uses Ag+ catalyst. The resulting polyelectrolyte has solubility and other characteristics significantly different from those of previously investigated poly(vinylsulfonic acid). This permits a study of the influence of the aromatic group on the local and long range interactions in solution. The barium salt of poly(styrenesulfonic acid) is unusual in showing both upper and lower consolute temperatures in solution.
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 611-629 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial deposition of homopolymers from solution [polyethylene, isotactic polystyrene, poly-3,3-bischloromethyloxacyclobutane (Penton) and polypropylene] was found on the (001) faces of cleaved alkali halide single crystals. Electron and optical microscopy studies have shown that the polymer usually grew from small, rodlike crystallites which were oriented in (110) directions of the halide crystal. Large oriented, four-leaved, “rose” structures also were observed for polyethylene. Electron diffraction studies indicate that the polymer chain axes for polyethylene, isotactic polystyrene, and Penton generally lie parallel to the (001) faces of the halide crystal and are also oriented in the 〈110〉 directions of the crystal face. Investigations on the effect of various halide substrates upon the epitaxial crystallization habit of polyethylene inferes that lattice matching does not play the major role in orientation. Two possible explanations are offered for this epitaxial behavior.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 631-638 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of basic aluminium dibenzoate upon the supercooling of polypropylene fractions of molecular weight 9.2 × 103-1.25 × 106 was determined by differential thermal analysis. The response to heterogeneous nucleation within the precision of the method used appears to be only slightly dependent, if at all, upon the molecular weight of the polymer.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 639-647 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wideline NMR techniques have been applied to both singly and doubly oriented specimens of nylon 66. Variations in the spectra obtained are observed for different orientations of the specimens relative to the applied field. These variations demonstrate that the zigzag chain axis is essentially parallel to the draw direction and that motion occurs in all of the sample. The motion is of two types: random in the mobile regions and rotation of segments about the chain axis in the rigid regions.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 659-662 
    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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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 663-665 
    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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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 649-657 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics of poly(n-octadecyl methacrylate) has been studied at the air-water interface. The rate of the crystallization has been measured by the decrease in the area of monolayers with time at various temperatures and surface pressures. The crystallization isotherms have been analyzed by the general mathematical treatment of the kinetics of phase changes, and the results show linear growth to be dominant. The variation of the rate constant with temperature and pressure has been illustrated by the difference in the supersaturation defined by introducing the equilibrium pressure-area isotherms.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 666-667 
    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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  • 53
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 668-672 
    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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  • 54
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 673-684 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Specific heats of plasticized poly(vinyl chloride) can be readily obtained by means of the thin foil calorimeter when the polymer is fabricated into sheet or film. The effects of temperature and plasticizer content on the specific heat and of the plasticizer content on the glass temperature are readily observed. The data may be used to estimate the glass temperatures of plasticizers where those temperatures are not readily reached by normal techniques. The specific heat at the glass temperature is approximately 0.255 for the ranges of 0-30 phr plasticizer. A definite glass transition is not observed with 60 phr plasticizer. No other transitions were observed between 200 and 400°K. The previous history of the polymer is important, as it can change the specific heat of the polymer noticeably, especially above the glass temperature. Comparison of the values listed here with those obtained by others should be made with the understanding that these samples were fabricated by extrusion and were free of observable strain. The degree of crystallinity of these polymers is very small, probably less than 10%, since none was found by x-ray diffraction. The plasticizing effect of some stabilizers was noted.
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  • 55
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 789-796 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical damping measurements were carried out in the range of 103-105 cps and between 60°K. and the softening point on some substituted Polystyrenes and poly(vinyl benzoates) containing different substituents (methyl groups, methoxy groups, and halogen atoms) either in the ring or in the main chain. The ortho and meta ring-substituted polystyrenes do not show any secondary mechanical relaxation in the glassy state, although all the other substituted polystyrenes, exhibit a low-temperature damping peak (δ process) (which is in some way connected with ring motions) whose height and temperature location depend on nature, position, and number of substituents. Substituents in the para position of the ring or in the α position in the backbone chain shift the δ peak of the unsubstituted polystyrene towards higher temperatures; this shift is accompanied by an increase of the apparent activation energy E*. Substitution in the β position, on the contrary, does not affect the δ peak. Analogous results are obtained for substituted poly(vinyl benzoates), which exhibit, in addition, a β relaxation effect, associated with carboxyl group motions. A very good correlation is found between the values of E* and the limiting relaxation time τ for the δ relaxation of polystyrenes and poly(vinyl benzoates), similarly substituted in the ring, indicating that the δ relaxation leads to absorption curves in the mechanical relaxation spectrum which are characteristic of the structure of the aromatic side chain.
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 817-825 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The vapor pressure osmometry method for determining the molecular weight of polyamides has been studied by use of the newly developed solvents. Polymers used were polycaprolactams, polyenanthamides, and polypelargonamides. The measurements were carried out with 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol as solvents at 50 and 130°C., respectively. Endgroup determinations on samples were also done in m-cresol by 0.1 N-hydrochloric acid. Reduced resistance differences (ΔR/C)0 obtained by vapor pressure osmometry at 50°C. were found to be in linear relation with the reciprocal of the number-average molecular weight determined by endgroup titrations; but anomalous results were obtained when dodecafluoroheptanol was used as the solvent at 130°C.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 923-942 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A light-scattering study is presented of two isotactic polypropylene samples with broad molecular weight distributions (Mw/Mn = 8.1 and 8.7, respectively) dissolved in α-chloronaphthalene at 147°C. Incident radiation of 5460, 4358, and 3650 A. was used. The reciprocal intramolecular scattering function, P-1(u) is expressed as a function of the variable [sin(θ/2)/λ′]2. This provides a wider range of experimental values of the variable u = 16π2(b2/6) [sin(θ/2)/λ′]2 than is accessible by the usual technique of using only one wavelength. The shape of the function P-1(u) is closer to that predicted theoretically if the weight distribution function f(N) in the equation \documentclass{article}\pagestyle{empty}\begin{document}$ P(u) = \int_0^\infty {Nf(N)P_N (u)dN} /\int_0^\infty {Nf(N)dN} $\end{document} is given by the log-normal distribution rather than the distribution function of Schulz and Zimm. The method is applicable to polymer samples for which the average molecular weights are too low to be measured by the light-scattering method of Benoit and Loucheux.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 943-949 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of highly crosslinked epoxyamine polymer networks with nonrandomly distributed crosslinks were investigated. The transition temperatures of these polymers can be correlated with the number of CH2 groups between crosslink junctions in the aliphatic amine portions of the network. The steepness of the modulus-temperature curve is also a function of crosslink density. This is in contrast with the case of natural rubber crosslinked by sulfur or by electron irradiation, where the modulus-temperature curves have similar shapes although the glass transition temperature increases with the degree of crosslinking. An empirical distribution function, similar to the one used by Tobolsky for stress relaxation distributions, was used to describe the temperature dispersion of the dynamic moduli. Two parameters, hg and hr, are used to characterize the steepness of the dispersion curve below and above the transition temperature, respectively. It is tentatively concluded that hg correlates with the length of the CH2 sequences in the amine portion of the polymer. The quantity hr may be related perhaps to the motion involving the trifunctional nitrogen junction.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 951-958 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The measurement of crystallinity and orientation in poly(ethylene terephthalate) is discussed. A simple procedure is given for the estimation of orientation from the (105) plane, and it is shown that methods which use the equatorial planes are subject to certain disadvantages. In addition a method is given for the measurement of x-ray crystallinity. The technique is applied to fibers and films of various treatments and a linear relation is found between density and x-ray crystallinity.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1013-1021 
    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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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 135-154 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new method of treating experimental data on the viscous and viscoelastic properties of various polymer melts is suggested. The dependence of the apparent viscosity on the molecular weight, temperature and shear stress can be represented as the product of three independent functions, each of them having a single argument. All three functions are universal, at least in first approximation, and the dependence of the apparent viscosity on the variables indicated is determined by two parameters (glass transition temperature and critical molecular weight), characteristic of each homologous polymer series. The viscoelastic characteristics (dynamic, relaxation, creep, as well as relaxation and retardation spectra) of polymer melts are universal in shape in the linear region and contain only one individual polymer parameter, viz., maximum Newtonian viscosity. It is shown that upon normalization of certain nonlinear characteristics with respect to the maximum Newtonian viscosity, they can also be represented in the universal form.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 158-160 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 199-208 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of five samples of poly(methyl methacrylate) covering a wide range of tacticity and their electron irradiation to produce series of varying molecular weight are described. The glass transition temperature Tg of each polymer was determined by DTA techniques. Plots of Tg and the reciprocal of the molecular weight are well fitted in every case by a straight line. The data are also fitted to the Gibbs-DiMarzio theory and the values of the energy and free-volume parameters obtained are discussed. A method of estimating Tg of pure syndiotactic poly(methyl methacrylate) by extrapolation is presented, the value obtained being 160°C.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 209-226 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The principles of a method are outlined whereby one can determine the partial specific volume of a solute, V̄, by means of measurements of dn/dc using a suitable pair of equations and a simple graphical interpolation procedure. The method yields V̄ data which compare well with densitometrically obtained V̄ data if the polarizability of both solvent and solute molecules is unaffected by the solution process. It is tested successfully on solutions of polystyrene in various solvents. The method appears to be particularly attractive for measurements of the change of V̄ with temperature and also for conveniently following the time rate of changes in - such as during the coil → helix transition.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 53-62 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethylene - propylene and ethylene - butene-1 copolymers with up to 1.7 side groups per 100 carbons have been crystallized at 227°C. and under 4100-4900 atm. pressure. The resulting crystalline polymers are at least partially of extended-chain crystal morphology. Comparison with the same polymers crystallized at atmospheric pressure, which gives folded-chain crystal morphology, revealed: (1) a density higher by 0.008-0.019 g./cm.3 depending on copolymer content; (2) a similar decrease of crystallinity with side group concentration; (3) a similar decrease of the beginning of melting from 125°C. for homopolymer to 65°C. for 1.7 side groups per 100 carbons; (4) a higher (138 ± 0.8°C.) experimental maximum melting point which, in contrast, is independent of copolymer content and seems to vary only with the fraction of low molecular weight material; (5) a decreasing amount of high-melting crystals with increasing copolymer content (72-8%) and an increasing amount of low-melting crystals (27-53%) with increasing copolymer content. In addition, superheating, which reached 5.5°C. for 50°C./min. heating rates, was detected. It was concluded that high-pressure crystallization leads, at least for part of the crystals, to solid solution formation, while atmospheric pressure crystallization does not. Which mode of crystallization is achieved seems kinetically determined. Experimental techniques were dilatometry, DTA, and calorimetry.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 299-311 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model of a rubber network formed from finite, linear polymer chains is treated, using expressions from accepted elastic theory as well as relationships that have been less generally used or only implied. The resultant empirical mathematical expressions conform very closely to the predictions of the simple kinetic theory of rubber elasticity and are mathematically consistent, in that the major properties and measurements are interrelated, and apparent inconsistencies in the literature are reconciled. As a consequence, an empirical equation is developed for the relationship between elastic properties and network structure in silicone gum vulcanizates. This equation is then applied to the estimation of peroxide crosslinking efficiencies.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 113-119 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A device for measuring the elasticity of polymer melts has been designed by one of us (B. Maxwell). The device was used to obtain the relaxation modulus in shear of a linear polyethylene melt. From these data a discrete relaxation spectrum was derived. The range of the obtained spectrum was confirmed to correspond to the terminal zone of the “entanglement plateau” of the spectrum. The limiting dynamic viscosity (as frequency approaches zero) was obtained by integrating the relaxation modulus with respect to time. The viscosity and its activation energy were found to agree closely with the flow viscosity and the flow activation energy, respectively, involved in capillary flow.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 121-133 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline polymers derived from cis- and trans-2-butene oxides were studied by x-ray diffraction methods. X-ray fiber and powder photographs of poly(trans-2-butene oxide) were indexed by an orthorhombic unit cell with the dimensions a = 13.72 A., b = 4.60 A., and c (chain axis) = 6.90 A.; the space group is P212121. The crystal structure of this polymer has been determined in projection. The chain has an erythro-diisotactic structure with -dl, dl- carbon sequences. The polymer has a nonplanar zigzag backbone with carbon and oxygen atoms of alternate monomer units lying nearly in a plane. Two chain molecules pass through the unit cell. The unit cell of poly(cis-2-butene oxide) is orthorhombic with lattice constants a = 11.20 A., b = 10.44 A., c (chain axis) = 7.01 A. The polymer has a threo-diisotactic structure with -dd,dd- or -ll,ll- carbon sequences. Four chain molecules pass through the unit cell. The crystal lattice is body-centered but the space group has not yet been established. The polymer has an almost fully extended zigzag chain configuration. Polymers prepared by either metal halide catalysts (FeCl3, SnCl4) or organometallic catalysts were essentially identical; the latter catalysts did, however, yield more highly crystalline polymers.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 155-157 
    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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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 161-171 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been shown that lamellar crystals of amylose V complexes with 71 helical configuration can be obtained by using complexing agents larger in cross section than n-butanol. The electron diffraction studies indicated a new unit cell for the unheated lamellar crystals which are composed of molecules with 71 helical configuration and hold water molecules on the exterior of the helix. Furthermore, from a throughly dried specimen at 100°C. in vacuo we obtained a pattern which showed only three Debye rings. Its spacings were explained by a two-dimensional hexagonal unit cell having a = b = 14.7 A. proposed by Zaslow. It was also found that when the crystals were dispersed in methanol at room temperature, their electron diffraction pattern was the same as that of the anhydrous amylose V complex of n-butanol.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 173-181 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationship of intrinsic viscosity to the number-average molecular weight has been obtained for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene in a few solvents. Values of (〈L2〉0/M)1/2 have been estimated for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene through the use of the treatment of Stockmayer and Fixman. The values of (〈L〉0/M)1/2 have been obtained as 2.18 ± 0.08 and 2.52 ± 0.07 for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene, respectively. The σ value of a series of polystyrene derivatives has been found to increase with the bulk of side groups. This seems to indicate that the σ value is mainly determined by the steric repulsion between side groups.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 183-198 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Good yields of some crystalline γ-alkyl esters of L-glutamic acid were obtained by carrying out the esterfication with a small (20-50 mole-%) excess of alcohol in aqueous hydrochloric acid or 60-80% sulfuric acid followed by neutralization with an alkaline solution. This new method made it possible to synthesize various γ-alkyl L-glutamates, including those higher than ethyl, and consequently, various poly(γ-alkyl L-glutamates) such as methyl, ethyl, n-propyl, n-butyl, isobutyl, and isoamyl. The conformation of these poly-L-glutamates in the solid state was determined by the infrared absorption method. The molecular motions of the polymers of γ-methyl, -ethyl, -n-propyl, -n-butyl, and-isoamyl L-glutamates and poly(γ-methyl-D-glutamate) in the solid state were studied by NMR, and dielectric and mechanical measurements. At temperatures up to 400°K., the NMR spectra of poly(γ-methyl D-glutamate) can be explained only by rotational motion of the side chain. Also, from NMR results, rotational motion of C=O groups in the side chain of poly(γ-methyl D-glutamate) is expected near room temperature, and such a motion was examined by dielectric measurements. Rotation of C=O groups in the side chains of polymers of γ-methyl, γ-ethyl, γ-n-propyl, γ-n-butyl, and γ-isoamyl L-glutamate was also observed near room temperature by dielectric measurements in the frequency range from 102 to 106 cps. Activation energies obtained by dielectric and mechanical measurements were similar to those for the side chain motions of the corresponding esters of poly(methacrylic acid). Although it has been noted that the molecular motion of poly(γ-benzyl L-glutamate) in the solid state at room temperature may be related to the motion of its back bone, the molecular motion in these poly-L-glutamates at these temperatures can be explained only in terms of side-chain rotation.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 423-435 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Short-range interactions between chain units of random copolymers in solution may be influenced by the composition or precisely by the distribution of sequence lengths of the same monomer units. Steric factors were derived for random copolymers of styrene and acrylonitrile with different compositions from the relation between the limiting viscosity number and the molecular weight. Mark-Houwink relations were obtained in methyl ethyl ketone (MEK) or in N,N′-dimethylformamide (DMF) at 30°C. for random copolymers containing 0.383 (Co-1) and 0.626 (Co-2) mole fraction of acrylonitrile, the expressions are: [η] = 3.6 X 10-4 Mw0.62, for Co-1 in MEK; [η] = 5.3 X 10-4 Mw0.61, for Co-2 in MEK; [η] = 1.2 × 10-4Mw0.77 for Co-2 in DMF. With the Stockmayer-Fixman expression, these correlations become, respectively: [η]/M1/2 = 1.24 × 10-3 + 8.0 × 10-7 M1/2; and [η]/M1/2 = 1.70 × 10-3 + 6.3 × 10-7 M1/2; and [η]/M1/2 = 1.68 × 10-3 + 31.3 × 10-7 M1/2. From the unperturbed mean-square end-to-end distances, 〈L2〉0, determined from the first terms of the latter expressions, together with 〈L2〉0f calculated by assuming the completely free rotation, gives the steric factor σ = (〈L2〉0/〈L2〉0f)1/2 as 2.25 ± 0.05 for Co-1, and 2.31 ± 0.10 for Co-2. These values of σ are close to those for polystyrene (σ = 2.22 ± 0.05) and for polyacrylonitrile (σ = 2.20 ± 0.05). Therefore, it is concluded that the dimensions of random copolymers of styrene and acrylonitrile in solution are not significantly influenced by the composition. In other words, the unperturbed dimensions are not affected by a change in the alternation tendency between styrene units with phenyl side groups having a large molar volume and acrylonitrile units with nitrile groups responsible for the electrostatic interactions. On the other hand, the long-range interactions reflect the effect of sequence length. The Huggins constant and the second virial coefficient obtained from the light-scattering measurements have optimum values at about 0.5 mole fraction of acrylonitrile, where the greatest tendency for alternation seems to exist.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 465-474 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Insertion poly(methyl acrylate) and poly(methyl methacrylate) were prepared from monomers adsorbed in monolayers on the surface of montmorillonite clay, both in the presence and in the absence of bifunctional crosslinkers (ethylene glycol dimethacrylate and tetramethylene glycol dimethacrylate). The insertion poly(methyl acrylate) and the crosslinked insertion poly(methyl methacrylate) and dilute-solution properties quite different from conventional polymers of these monomers, the differences including high light-scattering molecular weights combined with low viscosities, low values of the second virial coefficient, unusually large variations of the Huggins' constant k′ with the time-temperature history of the solutions, and low sedimentation velocities. These properties suggest that the insertion polymers have compact structures and are consistent with the postulate of sheetlike macromolecules. The dilute-solution properties of insertion poly(methyl methacrylate) made without crosslinker, unlike those of similarly prepared poly(methyl acrylate), were similar to those of conventional poly(methyl methacrylate). This difference in behavior is attributed to the different tendencies of the two monomers to undergo branching or crosslinking during radical polymerization.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 313-325 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of γ-irradiation and post-irradiation heat treatment on the specific volume versus temperature relationships of polytetrafluoroethylene (PTFE) samples (1/2-in. diameter rods) have been studied over the 40-150°C. temperature range for radiation doses up to 8.9 X 108 rad. At low doses the specific volume at any temperature decreased with dose, but above about 108 rad it increased with dose. Similarly, the rate of volumetric expansion initially decreased with dose, while, at very high doses (8.9 X 108 rad) the rate of expansion at temperatures above 100°C. exceeded that of the unirradiated PTFE. Heating at 150°C. for 100 hr. produced a substantial decrease in the specific volume and a decrease in the rate of expansion for the irradiated samples. Irradiation effects in PTFE are considered to be a result of such factors as radiation-induced chain scission, increased crystallinity, and increased void content. Changes resulting from post-irradiation heat treatment can be attributed to increased crystallinity, decreased void content, and weight loss.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 359-363 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature rise at the moving crack tip in poly(methyl methacrylate), resulting from the dissipation of the energy of crack propagation has been calculated. At velocities below 1 cm./sec., conduction of heat away from the crack plane into the bulk polymer appears to prevent any appreciable temperature increase.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 385-400 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 103-5.7 × 105. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 401-414 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl fluoride) polymers prepared at different polymerization temperatures have been examined in the melt, oriented, and solid state by infrared spectroscopy. Bands arising from the head-to-tail and head-to-head-tail-to-tail portions of the polymer have been isolated and assigned. The head-to-head-tail-to-tail portion of the polymer crystallizes in the head-to-tail unit cell except for a portion of the 1,2-difluorethylene units which apparently have the gauche (out-of-plane) structure. The head-to-tail portion of the polymer is nearly atactic, but is somewhat rich in syndiotactic chain structure. Bands arising from local syndiotactic order are observed.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 415-422 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Values of ε0ν0 the vaporization energy and volume in the hypothetical liquid state at 0°K., are derived for some simple polar and nonpolar molecules used as models for vinyl polymers. The following empirical relationship between the free volume fraction, f = (v - v0)/v, and the liquid compressibility coefficient β is demonstrated: -f2 ∝ This is applied to several vinyl polymer liquids near their glass transition temperatures, Tg, giving. fg ≃ 0.17, if the “hard-core” volume v* is considered to be independent of pressure and temperature, (i.e., v* = v0); or, fg ≃0.12, if the P,T dependence of v* is considered to be the same as that of the glass. These agree with fg values derived by Simha and Boyer from thermal expansion coefficients for the two analogous cases. An empirical viscosity-free volume equation of the Doolittle form: η = ATneb/f is applied to the glass transition, on assuming that this is an isoviscosity state and with the use of reported values for the expansion and compressibility coefficients and dTg/dP for three polymers: polystyrene, poly(methyl methacrylate), and poly(vinyl acetate). Reasonable values of b/n are thus obtained. This viscosity equation is critically examined in the light of molecular theories of liquid viscosity.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 697-704 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolarization currents were used to study the persistent polarization induced in polystyrene and poly(methyl methacrylate) by cooling with flow under pressure. These studies showed that the charge on electrets made by flow under pressure consists in part of a surface charge which leaks off rapidly in moist air and in part of a charge due to volume polarization which decays more slowly. The volume polymerization produced in poly(methyl methacrylate) by flow under pressure is of the same order as that produced by cooling under a voltage drop, but flow under pressure produces a larger surface charge.
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  • 81
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ability of various polymers to acquire persistent polarization (i.e., to become electrets) was investigated. Polarization was induced in the polymers by two methods: (a) by cooling under a voltage drop and (b) by cooling with flow under pressure. There was found to be an optimum temperature for electret formation by either method. This optimum temperature was roughly 37°C. above Tg when polarization was produced by application of a voltage drop and roughly 57°C. when polarization was produced by flow under pressure. Crystallinity and the nonhomogeneities present in blended polymers were harmful to electret formation, but a small critical amount of ionic impurity was helpful.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 705-714 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The determinations of the number-average molecular weight of polyethylene by cryoscopy has been improved, permitting precise measurements with both linear and branched polyethylenes in the molecular weight range 4,000-30,000. Improvements include a cryometer of new design, a lower-melting cryoscopic solvent containing a nucleating agent to control supercooling and rate of crystallization of the solvent, and more precise measurement of freezing point depression. Polyethylene samples are dissolved in hexamethylbenzene admixed with 0.1% of cadmium iodide, and steady-state freezingpoint depressions are measured with a thermistor to a maximum sensitivity of 5 × 10-5°C. Molecular weight measurements are reproducible to within ±10%. The cryoscopic apparatus and procedure are described in detail, and results obtained with samples of linear and branched polyethylene are presented and discussed.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 731-743 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gel permeation chromatography is an elution chromatographic process depending on the permeation of the solute through a bed of gel particles. This process is used in the estimation of molecular weight distributions of polymers, since elution occurs in decreasing order of molecular size. The eluting species, however, are not perfectly fractionated, and apparent broadening of the distribution occurs. This broadening results from an axial (longitudinal) mixing of the eluting species. Consideration of the accessible bed volume for each species permits a correction to be made for this axial dispersion. The concept was applied to heterodisperse distributions by solving the resulting simultaneous equations. A least-squares regression may be employed to utilize the experimental data most effectively. The experimental chromatogram can be described in terms of accessible bed volume and dispersion coefficient of each species together with flow rate, sample concentration, and chromatograph column geometry. The chromatogram corrected for the axial dispersion describes the molecular weight distribution more accurately than does the experimentally determined curve. The correction procedure was applied to a well-characterized polystyrene; the results of the gel permeation chromatography show excellent confirmation of the results of fractionation and of other instrumental analyses.
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  • 84
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Torsional creep measurements on four natural rubber vulcanizates, crosslinked to different degrees, were carried out in the temperature range from -50 to 90°C. This investigation complements the studies on identical samples of the stress relaxation behavior by Chasset and Thirion and of the dynamic mechanical response by Ferry, Mancke, Maekawa, Ōyanagi, and Dickie. The creep measurements reported are shown to be in agreement with the stress relaxation results. In addition to the usual temperature reduction, a superposed curve was obtained for the long time response using the apparent molecular weight between crosslinks, Mc, as a reduction variable. The variation in viscoelastic response with crosslink density is interpreted as a restrictive action of the chemical crosslinks on the transient entanglement network.
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  • 85
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization kinetics of crystalline fractions of propylene oxide polymers made with different catalysts have been studied by isothermal dilatometric and microscopical measurements. Isothermal microscopical measurements indicate that spherulite growth in these polymers proceeds from predetermined nuclei. The half time for spherulitic appearance is less than, but of the same order as, the half time for complete crystallization. Only by taking this factor into account can the dilatometric data be represented by the Avrami equation. The deviation of the crystallization isotherm from that predicted from the microscopical data using the Avrami theory is attributed to a secondary crystallization process taking place within the spherulite. Crystallization continues long after spherulites completely occupy the available volume in the polymer. By assuming that the secondary crystallization proceeds as a first-order process in the uncrystallized, but crystallizable, portions of the melt, it is shown that the crystallization isotherms can be completely described in terms of four parameters. These are: (1) the time constant for the primary crystallization process; (2) the time constant for nucleation; (3) the time constant for the secondary crystallization process, and (4) the extent of secondary crystallization. The important conclusions of these studies are: the rates of nucleation and of spherulitic growth are far more dependent on temperature than on stereoregularity; the ratio of the rate of the secondary crystallization process to that of the primary crystallization process is almost independent of temperature, but increases with increasing stereoregularity of the polymer.
    Additional Material: 8 Ill.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 765-775 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behavior of films of polyelectrolytes at the water-organic liquid interface depends on the nature of the interface and the pH of the substratum. The present paper investigates the influence of these two factors on the cohesive forces between monomer units. Two polyelectrolytes were studied: poly(methacrylic acid) (APM) and poly-2-vinylpyridine (2-PVP). In the case of uncharged films, the collapse pressure decreases when the polarity of the organic phase becomes more important, whereas the term ω/kT, which appears in the theory of Motomura and Matuura, increases. A quantitative relation between the parameter ω/kT and the collapse pressure may be deduced. The behavior of the ionized surface film at different pH values is modified by the choice of the interface. However, there exists a competition between two phenomena: the dissolution of ionized residues in the substratum and the electrostatic repulsion between charges in the surface plane. Depending upon whether the first or the second parameter is more important, we observed that the surface pressure decreased or increased with the degree of ionization.
    Additional Material: 6 Ill.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 777-788 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of polypropylene crystallized at pressures up to 5000 atm. has been studied. Upon slow cooling from the melt at 320 atm., the γ modification, previously found only in low molecular weight and stereoblock fractions, begins to appear in small amounts in addition to the normal α monoclinic form. As the pressure is increased further, a larger proportion of the sample crystallizes in the γ form until, at 5000 atm., only the γ modification is present. X-ray and DTA studies show that the γ form of polypropylene transforms to the normal α modification at a temperature only slightly below the γ melting point. Evidence is presented which favors the occurrence of a solid-state transition as a model of transformation to the α form. Results from isothermal crystallizations at low supercoolings and annealing experiments under high pressure show that the melting point of the γ modification of polypropylene is very sensitive to crystallite perfection.
    Additional Material: 3 Ill.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 797-816 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation behavior of stereoregular poly(vinyl alcohols) was investigated during stretching and after releasing the stress on the bulk polymers at relatively high humidity (80% R. H.) A structural model, differing from polyethylene, was proposed in which the crystallites were embedded in a considerably swollen amorphous matrix without any definite physical interaction so as to form an aggregation of crystallites, a superstructure. The crystal orientation followed, in principle, “the first borderline case” of Kratky, but with some difference from theory in orientation, while the noncrystalline orientation was represented by the freely jointed equivalent chain model of Kuhn and Grün with a value of N/γ as small as around 5. The difference between crystal orientation found and the theorietical orientation is discussed and some factors which prevented the crystal orientation are considered.
    Additional Material: 11 Ill.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 827-829 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 830-831 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 835-844 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The second virial coefficients of amylose acetate fractions have been determined at different temperatures and have been analyzed according to recent theories of second virial coefficient.
    Additional Material: 6 Ill.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 845-854 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic properties of 10 and 20% aqueous solutions of sodium polyacrylate were studied by the electromagnetic transducer method at 500 cps in the temperature range of 0-50°C. These solutions distinctly showed a relaxation phenomenon in this temperature range which was also affected by addition of such compounds as sodium chloride, urea, and dioxane. An anomalous behavior that cannot be explained as due to the relaxation phenomenon was observed on the addition of small amounts of these agents. One of the causes of this behavior is ascribed to the ion association in the solution. The static viscosity of the solution was also measured by using a rotating cylinder viscometer and the results compared with the dynamic data.
    Additional Material: 9 Ill.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 855-868 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transitions of an ionic polymer in bulk have been studied as a function of the counterion for various homo- and copolymers. It is shown that the glass transition temperature can vary by as much as 530°C., from -10°C. for the nonionic material to +520 for Ca2+ or Zn2+ substituted polymer. From simple electrostatic considerations, it is shown that a linear correlation should exist beween the glass transition and the ratio of the cation charge, q, to the internuclear distance, a, between cation and chain anion; for this particular material (the polyphosphate chain) the relation is Tg = 625(q/a) -12 where q is in units of one electron and a is in A. If the data are interpreted in the light of the Gibbs-DiMarzio theory, it is seen that both the chain stiffness and the intermolecular energy increase in an approximately parallel manner as q/a increases.
    Additional Material: 8 Ill.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1025-1027 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1029-1029 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 96
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    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 631-637 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triad distributions of 1,1-diphenylethylene (D)-methyl acrylate (M) copolymers have been determined from NMR measurements and examined according to the terminal and penultimate models of copolymerization theory. As expected from the diamagnetic shielding by the phenyl rings of the nearest D units, the methoxy proton resonances were found to appear as three resolved peaks at 6.4-6.6 τ, 6.7-7.0 τ, and 7.2 τ, and have been assigned to the central M units of the triads MMM, MMD or DMM and DMD, respectively. The copolymer composition and the triad distributions observed are shown to agree better with the terminal model with the methyl acrylate reactivity ratio of 0.092 ± 0.010 than with the penultimate model.
    Additional Material: 3 Ill.
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  • 97
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solubility properties of poly(vinyl alcohol) (PVA) vary with the method of preparation of the poly(vinyl acetate) (PVAc) from which it is derived. PVAc was prepared with free-radical catalysts over a range of temperatures from -78 to 90°C. with solvents of varying chain-transfer ability. The corresponding PVA samples varied in their resistance to dissolution in water. Their high-resolution proton nuclear magnetic resonance spectra showed on differences in tacticity. Data on 1,2-diol content showed only minor differences. Hence, the increase in resistance of PVA to dissolution in water arising from changes in chain-transfer activity of the solvent used in vinyl acetate polymerization is largely attributable to a decrease in molecular weight, and the increase in resistance of PVA to dissolution in water arising from a decrease in the temperature of the vinyl acetate polymerization is largely attributable to a decrease in both long and short branches. Evidently, with polar polymers having small side groups, tacticity is not the only factor influencing property variation; that is, variations in stereoregularity influence more the crystallinity of the sample as measured by density or x-ray methods than the ultimate crystallizability under conditions of mechanical and thermal treatment. In this regard polar polymers having small side groups differ from nonpolar polymers.
    Additional Material: 5 Ill.
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  • 98
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dissolution temperatures Ts have been determined for poly(vinyl alcohol) (PVA) samples of varying tacticity as a function of crystallization temperatures Tc. From the values of Ts and Tc, one can obtain values of (Tm)∞, the dissolution temperature of crystals of infinite stepheight. (Tm)∞ is a characteristic property of a given sample. This method of characterization is very sensitive and reliable for detecting differences in molecular regularity among PVA samples. The variation of (Tm)∞ with stereoregularity is attributed in part to differences in hydrogen-bonding characteristics. Determinations of the crystallinities of solution-crystallized PVA have shown that stereoregularity in PVA does not result in higher crystallizability.
    Additional Material: 1 Ill.
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  • 99
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    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 728-729 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 100
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    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 722-727 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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