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  • 1970-1974  (562)
  • 1970  (562)
  • Physics  (526)
  • Rat  (36)
  • Physical Chemistry
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1159-1168 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ESR and electrical conductivity measurements have been made on a recently prepared polymer, polypropiolamide. The polymer was obtained as a fine powder which exhibited a nearly Lorentzian line with a width between derivative maxima of 5.2 ± 0.1 gauss and a g value of 2.0036 ± 0.0005. The signal intensity increased with increasing molecular weight. The signal was retained in a dilute solution in formic acid with a slight narrowing of the line. Permanent changes were produced in the spectra at room temperature by heat treatments of the polymer at temperatures up to 800°K. The changes were similar for samples sealed in tubes containing air, dry nitrogen gas and a vacuum of 3 × 10-5 mm of Hg. Spectra obtained at temperatures up to 500°K showed no dependence on the presence or absence of oxygen in the ambient atmosphere. The deresistance of pressed pellets of the polymer was measured in the temperature range 450°K to 525°K, and the results were described by the relation R = R0cE/kT. The activation energy E had a value of 1.2 ± 0.2 ev and the resistivity at 500°K was approximately 1013 ohm-em. The ESR signal is attributed to an intrinsic property of the polymer which is associated with a conjugated bond system along the polymer backbone. Neither the activation energy nor the magnitude of the resistivity suggest that the delocalized electrons associated with the conjugated bond system have produced unusual electrical characteristics in the polymer.
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  • 102
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1235-1237 
    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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  • 103
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Critical miscibility data obtained from measurements of phase-volume ratios have been used to calculate the concentration dependence of the pair interaction parameter for the system polystyrene-cyclohexane. The measured temperature and concentration ranges are 11-30°C and 4-18% polymer by weight, respectively. With the Gibbs free energy of mixing expressed in polymer segment mole fractions, x*, the pair interaction parameter is g(x*, T) = 0.4961 + 71.92/T + 0.2312x* + 0.0750x*2. In a polymer volume fraction formulation the parameter is g(ϕ, T) = 0.4099 + 90.65/T + 0.2064 ϕ + 0.0518 ϕ2, which approximates to χ(ϕ, T) = 0.2035 + 90.65/T + 0.3092 ϕ + 0.1554 ϕ2. Comparison of the temperature and concentration dependence with that obtained by other authors shows very good agreement, even when extensive extrapolations in temperature and concentration are applied. The present function is believed to be the most accurate. Solutions of mixtures of two narrow-distribution polystyrenes in cyclohexane show separation into three liquid phases under the exact conditions predicted by theoretical calculation with the present pair-interaction function.
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  • 104
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1279-1289 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Selenacyclobutane (trimethylene selenide) readily undergoes photochemical reaction to give polymeric products. Also, the material polymerizes rapidly when the polycrystalline solid film liquifies on a salt substrate in vacuum. Upon polymerization of the sample, infrared and Raman spectra exhibit profound changes which definitely establish ring cleavage. The Raman spectra of the polymer reveal strong C-Se stretching peaks but little or no scattering in the region of Se-Se stretching, strongly suggesting that the polymerization process proceeds in a regular head-to-tail fashion. An EPR study of the monomer exposed to ultraviolet radiation at -180°C supports this fact, since the resulting spectrum is indicative of an intermediate radical species, (CH2CH2-CH2Se)n., where n is sufficiently large that the terminal electrons do not interact. No triplet spectra were observed. Molecular oxygen apparently plays an important role in the polymerization kinetics, since it is found that degassed samples of the substance, in contrast to those which have not been degassed, polymerize rapidly even under room illumination. Freezing-point depression measurements fix a lower limit to the average molecular weight of the polymer at 2700 (n = 23 monomer units).
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  • 105
    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 long-and short-chain branching in polymer molecules on gel-permeation chromatographic (GPC) separation is discussed. The calculation of calibration curves for branched polymers is developed from the universal calibration technique based on the hydrodynamic volume concept and previously established relationships for the effect of branching on molecular dimensions. Typical calibration curves are shown for different branching models and degrees of branching. As branching increases, the curves are shown to converge. Methods of characterizing branching and molecular weight distributions of franctions and whole polymers from GPC and intrinsic viscosity data are presented.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2177-2186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Branched polyethylene, melt-crystallized in commercial fabrication processes, cleaves into two layers when exposed to a prolonged “chemical filling” treatment (i.e., formation of filler in situ by interdiffusion of two reactive permeants). Cleavage has been observed in film and blown bottles. With film, progressive changes in experimental conditions from one sample to another, shifted the cleavage plane from near the surface to deeper lying planes. Separation of a thin surface layer requires more filler deposit than does separation into layers of more equal thickness. These observations suggest that a well defined layer structure may exist in branched polyethylene and that cohesive bonding is stronger between layers near the surface of the film than it is between deeper lying layers. Linear polyethylene showed slight layer separation after prolonged chemical filling, but clean cut separation of large areas was not achieved. This behavior may indicate that the cohesive bonding between layers is much stronger in linear polyethylene than in branched polyethylene.
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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1797-1801 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The current theoretical treatment of diffusion of gases in glassy polymers is based on the “dual sorption” model, but also includes certain other important assumptions, at least some of which cannot be fully justified a priori. They require experimental validation, which, however, is not possible by the procedures used or proposed so far. Methods suitable for this purpose are discussed here.
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  • 108
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1773-1786 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of the crystallinity of bulk polyethylene is calculated in terms of branching (methyl or ethyl side groups on the chain). In the model, the chains are approximately parallel and they pass through alternating amorphous and crystalline layers forming a periodic structure. The crystalinity and the thicknesses of the layers are determined by minimization of the free energy. The theory shows that the temperature at which the polymer begins to crystallize is lower than the melting point of pure polyethylene and that the thicknesses of the layers becomes smaller as the temperature decreases.
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  • 109
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1837-1839 
    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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  • 110
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1831-1835 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Average polymer segment densities and thermodynamic properties of polymer adsorbed at liquid-solid interfaces were computed by extension of the polymer adsorption theory of Forsman and Hughes. Expressions were derived for the total free energy of adsorbed polymer chains by using the Flory-Huggins theory to represent free energy of mixing. A square-well potential was used to represent segment-surface interaction, and configurational entropy was calculated from the probability density function for the radius of gyration of random-flight chains. For each specified amount of surface coverage the free energy of the adsorbed polymer was minimized by varying the density of segments normal to the adsorbing surface and using a modified gradient search algorithm on a digital computer. Two different segment densities were considered, and they both gave qualitatively the same results. The two densities were (1) the sum of two Gaussian distributions and (2) a two-step density distribution. Isotherms were then calculated by equating the partial molal free energy of polymer at the surface to that of polymer in bulk solution for each specified amount of surface coverage. The results showed that for the initial region of the isotherms the distribution of polymer segments normal to the surface consisted of a high-density layer adjacent to the surface and a low-density “tail” extending far out into the solution. At higher amounts of adsorbed polymer, i.e., in the general concentration range of the pseudo-plateau, the tail of the polymer density distribution was predicted to thicken, and a single Gaussian distribution best described the segment density. Predicted adsorptions were in good agreement with reported experimental values.
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  • 111
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1897-1908 
    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 molecular weight distribution on the viscoelastic properties of “entangled” polymers has been examined with blends of narrowly distributed polystyrene and broadly distributed polydimethylsiloxane. It is shown that blending laws established for nonentangled polymers do not apply to high molecular weight systems. The steady-state shear compliance of a blend is examined as a function of its molecular weight and the molecular weight of its components, and an approximation is given for the longtime viscoelastic response of entangled blends.
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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1927-1935 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The storage (J′) and loss (J″) shear compliances have been measured for two random copolymers of styrene and n-hexyl methacrylate with styrene contents of 18% and 30% (by weight) in the frequency range 45-4400 Hz and the temperature range 31-107°C. The data at different temperatures were combined by the method of reduced variables, and the WLF coefficients were calculated from the temperature shift factors by the method of Pierson and Kovacs. The data were compared with earlier data for the two homopolymers. The thermal expansion coefficient of the fractional free volume, and the free volume at the glass transition temperature, varied monotonically with composition, but the fractional free volume at a reference temperature of 100°C appeared to pass through a maximum as a function of concentration. Comparison of isothermal plots of J′ at 100°C, plots of the relaxation spectrum at 100°C, the monomer friction coefficient and its temperature dependence, and isochronal plots of the storage shear moduls at 100 radians/see all show that the properties of poly(n-hexyl methacrylate) are very slightly affected by incorporation of 18% styrene and only moderately affected by 30% styrene. By contrast, comparison of styrene-butadiene rubber with 1,4-polybutadiene shows a very large effect of incorporation of 23.5% styrene. These differences may be associated with local packing relations of the comonomer residues and suggest that copolymer properties cannot be readily predicted from those of the component homopolymers.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 401-410 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free radicals formed on irradiation of nylon 6 have been studied by means of electron spin resonance (ESR). The irradiation was performed at liquid nitrogen temperature with wavelengths in the region of solar radiation. The spectrum so obtained could best be fitted by assuming —CH2—ĊH—CH2— and —CH2—Ċ=O to be the trapped radicals. The assignment of the spectrum supports the idea that the first step in photodegradation is the breaking of the amide bond. The splitting constant of the α proton of the alkyl radical has been found to be nearly the same for drawn and undrawn yarn. This strongly suggests that the low-energy radiation is capable of breaking bonds only in the unoriented amorphous regions.
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  • 114
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 455-465 
    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 branched polyethylenes in the molten state were determined in the frequency range 10-3-10 radians/sec. The materials tested have remarkably similar rheological properties even though they vary greatly in molecular weight and molecular weight distribution. The similarity in properties is attributed to the influence of long chain branching on the relaxation spectra. A mechanistic argument is proposed to relate the observed behavior to molecular entanglement coupling. The concept of entanglement coupling involving long-chain branching leads to the expectation that the quasi-Newtonian and non-Newtonian viscosities of branched polymers may be either greater or less than those of linear polymers of the same species, which have comparable molecular weights. This is borne out by experiment.
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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 483-484 
    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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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 799-806 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile stress relaxation master curve for polyvinylcyclohexane (completely hydrogenated polystyrene) has been measured. Direct relaxation experiments were carried out at several temperatures above the glass transition temperature over the rather long time range of four orders of magnitude. This long time span was realized by calculating the modulus during the period when a constant small strain rate was applied to the sample as well as during the usual constant strain interval. A computer solution to the Boltzmann superposition equation allowed data from these two regions to be joined into a smooth curve representing E(t), a parameter indicative of an instantaneous strain experiment. The measured Ti was found to be 143°C; Tg is expected to fall within several degrees of this temperature. This result is apparently at odds with a previously reported Tg value of 120°C. More importantly, the maximum value of the negative slope of the stress relaxation master curve of polyvinylcyclohexane in the primary transition region was only slightly different from that for polystyrene. This observation clearly indicates that the molecular factors which result in the highly coupled nature of the primary transition in polystyrene are not strongly dependent upon any side-chain π-π interactions which might be present in polystyrene.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 791-797 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The NMR second moment of a uniaxially oriented mat of single crystals of n-C32H66 (in the orthorhombic form) was measured at temperatures from -170°C to 70°C and at various alignment angles γ between the orientation axis (preferential direction of the molecular chains) and the NMR magnetic field. Accurate expressions are given for the NMR second moment of an orthorhombic normal paraffin CnH2n+2 of arbitrary molecular chain length n for n ≥ 10, in the following states of molecular motion: no motion (a rigid lattice), rotation of CH3 groups, and rotation of the chains around their axes with superimposed rotation of CH3 groups. In addition to these well-known motions, n-C32H66 is found to exhibit an α process. The corresponding decrease of the NMR second moment shows the dependence on γ predicted for “flip-flop” motion, i.e., rotational jumps of the chain molecules around their axes through 180° and a simultaneous translation along these axes by one CH2 group. The overall decrease in second moment occuring at the transition to the hexagonal rotator phase in n-C32H66 can be quantitatively accounted for. The dependence of this decrease on the alignment angle γ, however, is in disagreement with calculations based on a simple rotation of the chains around their axes. Considerable torsion of the chains superimposed on the rotation would improve agreement between theory and experiment.
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  • 118
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 869-882 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics of a high molecular weight fraction of linear polyethylene was studied in dilute solutions of p-xylene, n-hexadecane, and decalin by dilatometric methods. For all solvents and temperatures, the experimental isotherms could be quantitatively described by the Avrami formulation for the complete transformation. This result is unique in the realm of polymer crystallization, since marked deviations from this theory are usually observed in more concentrated systems. The Avrami exponent is found to be n = 4 in all cases. The temperature coefficients of the rate constants are indicative of a nucleation controlled process. The data fit either a two-dimensional or three-dimensional nucleation mode, and a discrimination can not be made between these two cases. The interfacial free energies are found to be independent of the solvent medium. It is also shown that, irrespective of the type of nucleation control governing the kinetics, the same type governs the crystallite thickness of the lamella-like crystals that are formed.
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  • 119
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical properties of four kinds of natural rubber vulcanizates differing in vulcanization conditions, and consequently in degree of crosslinking (having values of the Mooney-Rivlin constant C1 ranging from 0.68 to 1.98) were observed under orthogonal biaxial stretching in a range of strain invariants Ii from 3.4 to 9.0 (extension ratios λi from 0.7 to 3.0). The results obtained were analyzed by two methods. One method employed the Valanis-Landel postulate that the strain-energy function W(λ1, λ2, λ3) is a separable symmetric function of the principal extension ratios, i.e., W(λ1,λ2,λ3) = w(λ1) + w(λ2) + w(λ3); the other utilized the contour plots of ∂W(I1, I2)/∂I1 and ∂W(I1, I2)/∂I2 surface within the (I1, I2) domain. The postulate for W was examined in detail with good agreement with experimental results. The dependences of ∂W(I1, I2)/∂I1 and ∂W(I1, I2)/∂I2 surfaces on the degree of crosslinking and temperature were further investigated, with the following conclusions. The surfaces have fairly steep slopes for the region of relatively small deformation (i.e., I1 〈 5) and become flat with increasing Ii for all the test specimens. The slope becomes less steep with decreasing degree of crosslinking. The values of ∂W/∂I1 increase linearly and the ∂W(I1,I2)/∂I2 surface becomes flat, both with increasing temperature: i.e., the temperature dependence of ∂W/∂I1 further depends on Ii. The ∂W(I1,I2)/∂I2 surface has a maximum near 40°C.
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  • 120
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1395-1409 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational contribution to the entropy of fusion was calculated for poly(ethylene adipate), poly(ethylene suberate), and poly(ethylene sebacate) from consideration of rotational potentials and steric interactions in model systems. An enumeration scheme similar to that applied to polyethylene was used. Comparison of the observed and calculated conformational entropies indicated the importance of a high-energy chain twist in the crystalline polyesters in reducing their measured conformational entropies. The rigidity of the polyester chains in the melt is discussed in comparison to polyethylene. The contribution of the polar ester groups to the heats of fusion of the polyesters is evaluated semiempirically.
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  • 121
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1425-1441 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The angular position of the extrema of the vertically polarized scattering intensity has previously been utilized for a method of particle size analysis for systems of monodisperse, spherical, isotropic particles which conform to the Rayleigh-Gans-Debye theory. The consequences of a finite polydispersity, which is always present in real systems, was not assessed and the application of the method has resulted in erroneous characterization of some latex systems. This work is concerned with (1) reporting the effects of finite polydispersity on the method of analysis, (2) pointing out previous misuse of the method, and (3) introducing a method of analysis which is based on the position of the extrema but which also considers polydispersity and the exact Mie calculation. This method enables one to characterize a scattering system in terms of a modal diameter and a distribution-width parameter by utilizing prepared diagrams for a particular relative refractive index.
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  • 122
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1467-1490 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It was established that polyethylene and polyoxymethylene crystallize epitaxially on NaCl cleavage faces over a temperature range in which the usual polymer single crystals dissolve but a crystallization memory remains due to very small quantities of self-seeding nuclei persisting in the solution. By performing this epitaxial crystallization in the presence of self-seeding nuclei, it could be established that epitaxial crystallization at these elevated temperatures involves only the very largest molecules in the distribution. Further, the self-seeding nuclei themselves could be isolated for observation, and these results were found consistent with previous predictions. By utilizing both the adhesion of these nuclei to NaCl and the selective nature of the epitaxial crystallization, the largest molecules could be extracted and reintroduced again to the same or different solutions. This opens up the possibility of a novel kind of chromatography for the separation and characterization of the highest molecular weight end of a distribution to a sensitivity which cannot be approached by other methods. The epitaxy phenomenon itself, under the circumstances involved, provides a new decoration method for the study of the surface topography of alkali halides. The origin of such as epitaxy occurring at low supercoolings and terminating at a limiting thickness raises important questions regarding long-range forces and some unsettled features in the theory of chain-folded crystal growth in polymers.
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  • 123
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polypropylene film was biaxially stretched in one step in air at 140°C or 152°C, and the deformation was studied optically. A linear relation held between Δnss and vA-½ for vA 〉 10, at both temperatures, where Δnss is the birefringence with respect to the normal to the film and vA is the degree of stretching expressed as the factor by which the area of the film is increased. Extrapolation of data in this linear region yielded a value of 20 × 10-3 for -Δnss at infinite vA. Since it is presumed that the polypropylene molecules lie completely parallel to the film surface when the film is stretched infinitely, -Δnss at vA-½ = 0 must be just half Δn°, the intrinsic birefringence in the case of completely parallel orientation. Thus, Δn° must be 40 × 10-3. This value was obtained experimentally in uniaxial stretching when the birefringence with respect to the direction of drawing was extrapolated to infinite extension. Similar relations held between np, the average of the refractive indices in the two stretching directions, and vA, and between nss, the index normal to the film, and vA. By similar extrapolations, (1/2)(n′γ + n′β) and n′β = n*α′ were estimated, and thence nα′ was obtained. Here, n′α and n′β are the refractive indices along the c axis (molecular chain axis) and b axis. All these optical parameters refer to a density of 0.900 g/cm3. Hence by applying a density correction to those values, the principal refractive indices and the intrinsic birefringence of polypropylene crystal were evaluated as follows: nα = 1.5522, nβ = n*α = 1.5106 and Δnc° = 4.16 × 10-3, where n*α is the refractive index prependicular to the b and c axes of the crystal.
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  • 124
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1617-1626 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The swelling curves of 6μ films of low conversion homopolymers and copolymers of acrylamide (AM) and N-isopropylacrylamide (NIPAM) were obtained in water by an optical microscope technique. Poly(AM) swelled appreciably faster than poly(NIPAM) but there was no apparent correlation between overall swelling rate and copolymer composition. A 57/43 (mole %) AM-NIPAM copolymer swelled fastest. Sequence distribution calculations indicated that its backbone structure tended toward comonomer alternation, which might reduce the extent of hydrogen bonding in the film. The amount of water sorbed during swelling, as approximated from increasing film thickness, was proportional to the square root of time and agreed well with previous work in the literature. Homopolymer films from runs of ca. 50% conversion consistently swelled slower than their low conversion counterparts, probably due to branching and increased entanglements. Heating also promoted slower film swelling due to a tightening of the film structure and/or a low degree of imidization. Monomer reactivity ratios and Alfrey-Price Q and e values for NIPAM were calculated. Cloud points of 5% aqueous solutions of the copolymers were measured and found to decrease with increasing NIPAM content.
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  • 125
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1637-1637 
    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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  • 126
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1661-1678 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of crystals in spherulites of modifications I and II of polybutene-1 was studied by micro-x-ray diffraction. Changes in such micro-x-ray diffraction patterns were measured in various regions of the spherulites as a function of strain and time. The relationship between micro-x-ray diffraction from parts of spherulites and macro-x-ray diffraction from entire spherulites is discussed. Changes are resolved into contributions arising from (1) deformation of spherulites with change in crystal orientation and (2) transformation of crystals from modification II to modification I.
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  • 127
    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 nylon 3 was studied, and four crystalline modifications were observed. Modification I, as determined from the x-ray diffraction pattern of drawn fibers, is similar to the α crystal structure of nylon 6. The unit cell is monoclinic; a = 9.33 Å, b = 4.78 Å, (fiber identity period), c = 8.73 Å, and β = 60°. The theoretical density for nylon 3 with four monomeric units in the unit cell is 1.39 g/cm3, and the observed density is 1.33 g/cm3. The space group is P21. The nylon 3 chains are in the extended planar zigzag conformation. Although other odd-numbered nylon form triclinic or pseudohexagonal crystals when oriented, drawn nylon 3 crystals are monoclinic. In addition to modification I, modifications II, III, and IV were studied. Lattice spacings of modifications II and III are equal to those of modification I. However x-ray diffraction intensities are different. Infrared spectra of those forms indicate an extended planar zigzag conformation of the chains. Modification IV is thought to correspond to the so-called smectic hexagonal form. No γ crystals were found, and it appears that polyamide chains with short sequences of methylene groups cannot form crystals of this type.
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  • 128
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 991-998 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion of 1,1-diphenylethane in trace amounts through eight rubbery polymers has been studied by radioactive tagging of this penetrant with 14C. For several polymers, the dependence on temperature and on dilution (swelling) by untagged diphenylethane was investigated. In the diluted systems, tagged n-hexadecane was also used as a trace penetrant. The temperature and concentration dependences were interpreted rather successfully in terms of the free volume. In comparing different polymers, with a 4000-fold range of diffusion coefficients, the translatory friction coefficient of 1,1-diphenylethane was found to be proportional to that of n-hexadecane to the power 1.06. This is interpreted qualitatively by the free volume concept to indicate a slightly less efficient mobility mechanism for the diphenylethane.
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  • 129
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1415-1424 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mutual diffusion of pairs of polymers has been studied at 160°C for two systems: isotactic polypropylene with polyethylene and poly(vinyl chloride) with polyethylene. From the assumption that Fick's law is valid and with a rhombohedral lattice model for the microheterogeneous system, it was possible to obtain from volume changes the thickness of the interphase layer after various diffusion times. It was found that the values so calculated differ considerably from the experimental values, the greatest deviations occuring after 20 min diffusion. From this it follows that non-Fickian diffusion strongly influences the distribution of concentrations in the diffuse interface, and thus affects the calculated value of the interphase layer thickness. For both polymer pairs Fickian behavior was confirmed for up to about 10 min diffusion time, in good agreement with experimental data.
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  • 130
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1503-1519 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A statistical theory for the scattering of light from oriented polymer films is developed in terms of angularly dependent generalized correlation functions. Numerical calculations of scattering patterns are carried out for special cases. The scattering depends upon two types of distributions describing (1) the orientation distribution of optical axes of scattering elements and (2) the angular dependence of correlation in orientation between pairs of optic axes. These distributions are expanded in Fourier series (in a two-dimensional treatment), the coefficients of which are functions of elongation and describe the elongation dependence of the scattering patterns.
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  • 131
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1845-1845 
    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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  • 132
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1885-1896 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new light scattering photometer has been designed in order to perform light-scattering measurements at various temperatures and under pressures of 1-1000 atm. Since the scattering angle is constant (90°C), the dimensions of the dissolved molecules are determined by measuring the intensity at different wavelengths. The method of measurement, the calibration of the instrument, and the treatment of data are described. By a series of test measurements on polystyrene in trans-decalin solutions it is shown that one obtains reliable results and finds considerable effects of pressure on the radius of gyration and the fundamental thermodynamic properties of the system.
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  • 133
    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 methacrylate) (PMMA) formed within a monolayer of monomer adsorbed on montmorillonite was studied by means of NMR spectroscopy and shown to be composed of short stereosequences with a predominant isotactic component. The stereospecificity of the insertion PMMA can be understood in terms of the organization of the monomer adsorbed on the surface of the mineral. The monolayer of monomer is assumed to be composed of monads and isotactic diads due to dipole-ion interactions between the molecules of methyl methacrylate and exchangeable cations. Results of experiments relating factors such as temperature, density of ion population of the surface, and the nature of ions are discussed. It is shown that the populations of isotactic and syndiotactic triads Pi and Ps determined experimentally in the insertion PMMA are in a reasonable agreement with values calculated from the model. It is shown, furthermore, that Pi increases with increase in the density of the ion population, in agreement with the equations derived from the model.
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  • 134
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1637-1637 
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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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  • 135
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1443-1456 
    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 varying molecular weight distribution on the self-seeding phenomenon was investigated by using high molecular weight polyethylene fractions prepared by the stirring-induced crystallization method of Pennings. The numbers of self-seeding nuclei per gram were determined by measuring crystal dimensions, and were found to increase with increasing molecular weight of the polymer, in accord with previous findings. In another experiment, self-seeded single crystals were grown from materials of various molecular weights, prepared by blending two samples of differing molecular weight in various proportions. The concentration of nuclei varies linearly with the weight fraction of high molecular weight polymer in the mixture. This result is shown to be consistent with the proposition that each nucleus contains on the average an identical number (most plausibly one) of molecules of very high molecular weight. The application of this finding to the determination of molecular weights is discussed, and it is shown that the technique provides a method of unprecedented sensitivity for the characterization of the very high end of the molecular weight spectrum. Some morphological results are also presented. In particular, direct observations of the nuclei were found to be consistent with the loosely connected multiple nucleus structure, which had been proposed previously to account for certain light-scattering results.
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  • 136
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1575-1584 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The resonance frequencies of unidirectional carbon fiber reinforced/epoxy composite beams were studied over the temperature range 24-225°C. Longitudinal Young's moduli E11 and longitudinal-transverse shear moduli G12 were computed from the experimental data by the use of Timoshenko beam theory. The effects of transverse shear deformation (a function of E11/G12) were found to increase in importance with increasing temperature. Values of G12 were found to be approximately proportional to the shear modulus Gm of matrix material but were about 30% lower than predicted by the theory of Hashin and Rosen. The anisotropy of the carbon filaments and voids in the composite samples were proposed to account for the discrepancy between theory and experiment.
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  • 137
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1635-1635 
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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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  • 138
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1639-1649 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The general problems presented by the determination of the optical activity of polymers in the crystalline state are considered. The necessity of using unoriented samples, if the polarimetric data are to be compared with analogous data measured in solution, is emphasized. The optical activity in the crystalline state of a number of stereoregular vinyl polymers has been measured by employing either suspensions of fine powders or thin plates with no detectable orientation. The results of optical rotatory dispersion studies in the crystalline state suggest that, at least in the case of the poly-α-olefins investigated, the same chromophores are responsible for the optical activity in the crystalline state and in solution.
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  • 139
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1697-1701 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Middle range fractions of mimusops balata, a natural trans-1,4-polyisoprene, exhibit transcrystallinity when crystallized in the 35-40°C range. The presence of transcrystallinity was established by x-ray diffraction and optical microscopy. Diffraction peak intensities change due to transcrystallinity, suggesting x-rays be used to detect transcrystallinity and that caution be exercised in using x-ray diffraction techniques to determine the phases present in bulk material and in calculating the degree of crystallinity. The tendency toward transcrystallinity may depend upon molecular weight.
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  • 140
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1723-1740 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transformation of microspherulitic quenched and annealed polyethylene film into highly oriented drawn material with the characteristic fiber structure was investigated by small-angle and wide-angle x-ray measurements and by a study of the thermograms after the fuming nitric acid treatment. With the details of deformation depending slightly on the crystallinity, one observes generally a preferential tilt of the platelets against draw direction at draw ratios below 2. At least in annealed material, an increasing tilt of the molecule within the lamella is also observed, which leads at higher draw ratios to slipping of blocks in the crystallites. With further drawing a new fiber structure appears, which is practically independent of the thermal history of the original film. This fact is established by investigation of the crystal thickness by three different methods; investigations of small-angle scattering, study of the width of the (002) reflection, and investigation of the debris after treatment with fuming nitric acid.
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  • 141
    ISSN: 1591-9528
    Keywords: Hepatic microcirculation ; Intravital microscopy ; Haemorrhagic hypotension ; Rat ; Mikrozirkulation der Leber ; Intravitalmikroskopie ; hämorrhagische Hypotension ; Ratte
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Auswirkungen eines massiven Blutverlustes auf die Blutströmung in den Sinusoiden der Leber bis zum Zusammenbruch der Mikrozirkulation sind fÜr das Ausmaß und die Reversibilität der akuten Blutungsfolgen wesentlich. Während kontrollierten Entblutens wurde bei der Ratte an einem vorgelagerten Leberlappen die Mikrozirkulation intravitalmikroskopisch im Durchlicht beobachtet. Durch die Anwendung einer Modifikation vorliegender Methoden waren gleichzeitige Druckmessungen in der Vena portae und in einer Arteria carotis möglich. Die gewonnenen Ergebnisse bestätigen die Brauchbarkeit der Versuchsanordnung. Zu einem vollkommenen Strömungsstillstand in allen sichtbaren Sinusoiden kommt es nach langsamem Entbluten von durchschnittlich 30% des Blutvolumens. Der Druck in der Arteria carotis ist dabei von 89,25 auf 21,4 mm Hg, der portale Druck von 92,3 auf 31,4 mm H2O abgefallen. Die Korrelation zwischen dem arteriellen und dem portalen Druck bleibt während dieses Abfallens erhalten.
    Notes: Summary The sequels of a massive haemorrhage on the blood flow in the sinusoids of the liver until the microcirculation breaks finally down, are essential for the degree and the reversibility of acute complications of the haemorrhage. The microcirculation of the exposed rat liver has been observed by intravital microscopy by means of transillumination during controlled desanguination. A modification of methods previously used made it possible to measure simultaneously systemic and portal blood pressure by portal and carotic arterial catheters. The results obtained proved the reliability of the method. A complete flowstop in all visible sinusoids has been observed after slow drainage of 30% of the blood volume. At this stage the blood pressure in the carotic artery has decreased from 89.25 to 21.4 mm Hg and the portal pressure from 92.3 to 31.4 mm water. The correlation between the arterial and the portal blood pressure remained unchanged during this decrease.
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  • 142
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    Clinical and experimental medicine 152 (1970), S. 352-355 
    ISSN: 1591-9528
    Keywords: Aurothiomalate ; Penicillamine ; Diethylenetriaminepentaacetate ; Rat ; Aurothiomalat ; Penicillamin ; Diäthylentriaminpentaacetat ; Ratte
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wurde der Einfluß der D- und L-Isomeren von Penicillamin sowie von Diäthylentriaminpentaacetat auf die Organverteilung von Gold bei der Ratte untersucht. Während Diäthylentriaminpentaacetat sich als unwirksam erwies, wird Gold durch Penicillamin in nur geringem Maße mobilisiert. Der klinische Wert von Penicillamin als mögliches Antidot bei der Chrysotherapie erscheint somit fraglich.
    Notes: Summary The influence of the D- and L-isomeres of penicillamine as well as of diethylenetriaminepentaacetate on the distribution of gold in the organs of the rat was studied. Whereas diethylenetriaminepentaacetate proved to be ineffective, penicillamine brings about a marginal mobilization of gold only. The clinical value of penicillamine as possible antidote in chrysotherapy, therefore, is doubtful.
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  • 143
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 679-687 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermodynamic functions of ten monomeric compounds have been calculated for three temperatures by the statistical method using molecular structural data and vibrational assignments. The ideal gas state entropies at 298.15°K are: maleic anhydride, 71.9; β-propiolactone, 69.1; vinylene carbonate, 70.1; cyclopentadiene, 65.3; diketene, 72.3; cyclopropene, 58.7, vinyl fluoride, 60.4; ethyleneimine, 62.8; butatriene, 71.7; and carbon suboxide, 66.0 cal./deg-mole. The standard free energies and equilibrium constants of formation are also derived by using mostly the published data on the heats of formation of these monomers.
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  • 144
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1039-1056 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of inferring molecular weight distributions from concentration gradient data taken at sedimentation-diffusion equilibrium for a single rotor speed is ill posed: significantly different distributions correspond to concentration gradients which differ so slightly that they cannot be distinguished by the experiment. It is this intrinsic property of the problem which accounts for the lack of success of the several schemes proposed for its solution. Integral equation theory is applied to show explicitly just what can be inferred with bounded error. Several methods for recovering this information are discussed and applied to example problems.
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  • 145
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1089-1110 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gelation of poly(methacrylic acid) in water was studied as a function of degree of neutralization with NaOH. It was found that charging the molecular displaces the onset of gelation to higher concentrations but makes the transition occur over an even narrower concentration range. This extreme sensitivity of rheological properties to charge may play a role in biocolloidal systems. The phenomenon of reversible gelation is discussed in general and related to the properties of the particular system. The method of measurement, which involves the determination of the dynamic response in the 1 Hz region and the measurement of phase angle, is described in detail. A method of deriving the relaxation time spectrum from measurements of phase angle is given.
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  • 146
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1169-1175 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-4,4′-oxydiphenylenesulfonyl and poly-4,4′-methylenediphenylenesulfonyl were synthesized by an electrophilic substitution polymerization of the arylene monosulfonyl chloride monomers. The glass-transition temperatures Tg of these polymers were determined by calorimetric and dynamic mechanical measurements, and the number-average molecular weights were determined by vapor-pressure osmometry. Both polymers were found to have the same Tg at equivalent molecular weight; the limiting value at high molecular weight is 238°C. Both polymers have two dynamic mechanical relaxation peaks at temperatures far below Tg. One is in the neighborhood of 0°C, and the other is at -110°C. Plausible origins for these relaxations, and the absence of any near 0°C in poly(4,4′-isopropylidenediphenylene-co-4,4′-sulfonyldiphenylene dioxide), are discussed.
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  • 147
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1971-1985 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isotactic 3-methylbutene homopolymers and copolymers (of low 1-olefin content) exhibit a major transition between 50 and 100°C, which dilatometric, density, and NMR observations indicate is not a glass transition, but rather a crystal-crystal transition occurring within the crystalline phase, the only phase present in significant amount. Fibers prepared from these polymers show a very high degree of orientation and crystallinity, have measured densities close to the theoretical crystal densities, and exhibit abrasion debris and electron microscopic evidence of crystalline lamellae. The fibers have a quasistatic initial modulus equivalent to the sonic modulus and exhibit very low stress relaxation and very high elastic recovery from large extensions. The fact that the fiber is highly crystalline and fully oriented, with a comparatively low initial modulus, high elastic recovery, and an extensibility of about 40%, indicate that the crystalline lamellae themselves, joined together in stacks, are able to deform (probably bend) elastically, and that the aggregate is able to undergo large elastic deformations.
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  • 148
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1987-1997 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experimental technique for the simultaneous measurement of solubility and diffusion coefficients in polymers by frequency response techniques has been developed. A sample of polymer suspended from an electrobalance is exposed to a permeating gas whose pressure is being varied sinusoidally at ultra-low frequencies. The phase angle and amplitude of the weight changes are measured as a function of the frequency of the pressure wave. It is shown that in the linear range the diffusivity coefficient for polyethylene-ethane calculated from the phase angle lag and the Henry's law solubility and the diffusivity obtained from the amplitude ratios are in excellent internal agreement and also agree with values obtained from transient measurements.
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  • 149
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2015-2027 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The experimental observation of an isotope effect in diffusive gas transport across polymeric films is reported. The differences in energies of transport between hydrogen and deuterium are used to estimate the effective dimensions of characteristic minima or “wells” in the potential energy surface of rubbery polymers. The size of a well, determined by assuming it to be a cubical cavity, is interpreted as the effective free volume element vf, as measured by the hydrogen molecule probe. Estimations are made of the entropy of activation and “jump distance” for the hydrogen diffusion process based on vf values and experimentally determined pre-exponential factors.
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  • 150
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2089-2094 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on dilute solutions of a pyrrone “prepolymer” are presented and the tendency of this polymer to aggregate in certain solvents commonly used in dilute solution studies is discussed. It is concluded that reliable molecular weights can be determined if solvents that interact with the prepolymer through hydrogen bonding are used.
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  • 151
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2115-2126 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The calculation of the scattering from a sheaflike sector of a two-dimensional spherulite has been carried out as a function of the apex angle of the sector. It is found that while for a complete spherulite the Hv scattered intensity is zero at zero scattering angle, there is an increasing intensity of scattering at 0° as the sector angle narrows. For very small values of the sector angle, the scattering becomes similar to that of a rod, with the exception that a scattering maximum is still seen at an angle close to that at which the spherulite scattering maximum occurs. The predictions of the model compare favorably with the scattering patterns observed for polymers in early stages of spherulitic growth.
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  • 152
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2153-2161 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of elemental selenium has been studied in light of present concepts of crystallization in organic polymers. Bulk-crystallization kinetic data as measured by a dynamic density technique and spherulite growth-rate data as measured by optical microscopy are presented for the temperature range 70°C to 160°C. Plots of extent of isothermal crystallization versus time were sigmoidal in shape. Spherulite growth rates were constant for a given temperature and reached a maximum at approximately 130°C. Evidence is presented for secondary crystallization in selenium, and a model is proposed for destruction of chain folds with interlamellar crystallization during the spherulitic-to-“metallic” transformation above 100°C.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2187-2195 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have observed a flow of charge on illumination of low-density polyethylene with infrared light in the wavelength range 1.6-0.7 μ by using silver electrodes. This flow is reversed on removal of the light, is proportional to the light intensity, and varies little with wavelength in this spectral region. There is no significant response to light of visible wavelengths. The effect decreases as the temperature is increased up to 60°C, though the time constant remains fixed. There are qualitative differences between the responses obtained with gold and with silver electrodes, and quantitative changes when the ambient air pressure is altered. The behavior suggests that during illumination, the dynamic equilibrium between carriers in the electrodes and those in the material close to the electrodes undergoes a reversible adjustment.
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  • 154
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2051-2065 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The NMR relaxation times T1 and T2 have been measured for fractionated samples of polydimethylsiloxane with different molecular weights in the amorphous state and in tetrachloroethylene solutions. The results are interpreted on the basis of the anisotropic reorientation model proposed by Woessner for small molecules. A correlation time characteristic of the diffusional rotation of chain segments is calculated and shown to be proportional to the square root of the bulk viscosity.
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  • 155
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2067-2078 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An elastic-fluid theory of die-swell for long dies is presented. The theory predicts a swelling ratio De/d asymptotically proportional, for large values of swelling, to the cube root of the recoverable shear evaluated at the die wall. Here the recoverable shear is defined to be half the ratio (first normal stress difference/shear stress). Excellent agreement is shown between predicted De/d and measured De/d for experiments on melts and solutions for which adequate data are available.
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  • 156
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2079-2087 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The unit-cell dimensions and density, at room temperature, of bulk- and solution-crystallized linear polyethylene have been determined. The macroscopic measured densities for the bulk-crystallized samples ranged from 0.917 to 0.993 g/cc, and the lattice parameters were found to be independent of the sample density. In contrast, for solution-formed crystals, despite the limited range in macroscopic densities that can be attained, there is a systematic variation in the a and b dimensions with the measured density and the crystallite thickness. The implication of these results for the calculation of the degree of crystallinity and the interpretation of certain infrared bands are discussed.
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  • 157
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2163-2175 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We present the results of accurate numerical solutions to the Lamm equation, including the effects of hydrostatic pressure, in order to check methods for the estimation of parameters based on a diffusionless theory. Some estimates of boundary spreading due to diffusion are given. The results indicate that parameter estimates based on the position of the maximum concentration gradient lead to fairly accurate results.
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  • 158
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 555-570 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four equations, relating the glass transition temperatures Tg of homopolymers and copolymers to invariant additive temperature parameters (ATP) associated with their constituent groups, but weighted in different ways, have been applied to the calculation of the Tg of seven series of polymers having alkyl side chains. It is shown that the Tg of the 32 polymers considered may be calculated, within 7°K of the observed values, without the use of interaction coefficients from 15 independent variables, representing summations of the ATP's. The present calculations are confined to those structures which may be formed by a recombination of the structures corresponding to these independent variables. It is an essential feature of the approach that a distinction is made between groups with different nearest neighbors. Alternative methods of calculation are considered. The temperature parameter for a sequence of three or more methylene groups is estimated as 141°K, in conformity with the transition in polyethylene at 148°K. Nearest-neighbor interactions, stereoregularity, and crystallinity effects are discussed.
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  • 159
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 625-635 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of chain entanglement in undiluted linear amorphous polymers is treated by calculating the probability of forming closed intramolecular loops. Adoption of the rotational isomeric state model of polymer chains permits an appropriate accounting of the detailed molecular structure to be made through the configurational characteristics of the polymer. The second (〈rhk2〉0) and fourth (〈rhk4〉0) moments of the vector rhk connecting groups h and k in the isolated polymer chain and averaged over all chain conformations are calculated and used to evaluate the probability Wx(0) that rhk is 0, or that an intramolecular loop of x = k - h bonds is formed. Several linear polymers with widely differing molecular structures are treated. An attempt is made to correlate the degree of chain entanglement they manifest in the bulk with their ability to fold back upon themselves to form closed intramolecular loops.
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  • 160
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 643-648 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 161
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 713-726 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methacrylic acid) has been studied in 0.002N HCl-ethanol mixtures as a function of molecular weight. A different dependence on molecular weight is noted at different alcohol concentrations. Since the intrinsic viscosity passes through a series of extrema with changes in alcohol concentration, the dependence on molecular weight has been considered in two regions of alcohol concentration in particular. The region of the first minimum and the region of the second minimum (or overall maximum). In the region of the first minimum, intrinsic viscosity is proportional to M½, just as in 0.002N HCl. The Huggins coefficient k′ is large (ca. 60) but drops to about 10 when the molecular weight exceeds 320,000. In the region of the second minimum the dependence on molecular weight is complex. Intrinsic viscosity is proportional to molecular weight both at low and at high molecular weight and thus indicates freely draining structures. There is a conformational contraction, however, at molecular weight about 320,000 leading from one type of structure to the other. The structure at higher molecular weight may involve a specially strong bond between specifically grouped segments in the chain. The positions of the extrema along the alcohol concentration axis are not molecular weight dependent, particularly above 320,000. Results available for molecular weight dependence in methanol agree well with this picture. The present results confirm prediction inherent in the model of Silberberg and Priel and Silberberg.
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  • 162
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 753-770 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several molecular mechanisms, proposed in the literature for the low- and high-temperature relaxation processes in linear polyethylene and commonly referred to as γ and α processes, are examined, and their effect on the second moment of the broad line NMR absorption is predicted quantitatively. The following models for the α process are discussed: rotational oscillation of the long chain molecules around their axes, general two-site models where the chain performs thermally activated rotational jumps through an angle τ between two equilibrium positions, a particular two-site model (τ = 180°) denoted as flip-flop motion, and the kink model. For the γ process, the following molecular mechanism are considered: the kink model, a vacancy with a chain end, the crankshaft mechanism. The decrease of the second moment caused by these motions is considered. Characteristic differences between the motional models are predicted with respect to the anisotropy of the decrease in second moment in a uniaxially oriented sample and/or the magnitude of the overall decrease. These differences allow an experimental distinction between the different models.
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  • 163
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 833-839 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A chromatographic technique is described where the stationary phase is a layer of a very high molecular polystyrene fraction (M = 107) on glass beads (ballotines). The mobile phase is cyclohexane passing the column at a constant temperature below the theta-temperature. A polystyrene sample of sufficiently low molecular weight (M ≤ 106) injected as a small plug at the top of the column is fractionated because the distribution between the mobile and the stationary phase depends on the molecular weight. Since the large molecules preferentially remain in the stationary phase, the smaller molecules leave the column first. The fractionation effect is inverse to that found in GPC experiments. The separation efficiency is rather good and can be described by a simple thermodynamic theory.
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  • 164
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The unperturbed chain dimensions of unfractionated poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly-(2,6-diphenyl-1,4-phenylene oxide) have been measured by combining molecular weight data from light scattering with intrinsic viscosity data in chloroform. The unperturbed chain dimensions of the former polymer were also measured directly by light scattering dissymmetry in a critical consolute solvent mixture (methyl cyclohexane: 1,4-dioxane 50:50 by volume). The results of these measurements and of measurements reported by other investigators are satisfactorily explained by postulating no dimension-expanding prejudice in azimuthal angle in chain conformers of the 2,6-substituted-1,4-phenylene oxide polymers. This corresponds to equal population of the two chain rotation energy minima at azimuthal angles 90° and 270°. Accepting this postulate, one calculates from the observed chain dimensions that the C—O—C bond angle is 118-120° in these aromatic polyethers in solution.
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  • 165
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 937-955 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of homogeneous nucleation of bubbles is combined with an expression, for their rate of growth in elastomers to obtain approximate expressions for calculating the number of bubbles formed under a high degree of supersaturation. Experimental results are given for several elastomers with argon as the dissolved gas under a variety of foaming conditions. The theory adequately describes the manner in which the number of bubbles formed depends on the temperature, surface tension of the polymer, and permeability of the dissolved gas.
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  • 166
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1011-1013 
    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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  • 167
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1227-1233 
    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 proposed for use of the universal calibration curve, i.e., the product of molecular weight and intrinsic viscosity versus retention volume, in calculating the molecular weight distribution of a polymer from gel-permeation chromatography (GPC) when the Mark-Houwink relation of the polymer in the solvent used for the GPC is unknown. This is achieved by measuring the viscosity of each fraction with an automatic capillary tube viscometer. Application of this technique to poly(vinyl chloride) and poly(vinyl acetate) proved to be successful.
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  • 168
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1239-1259 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of periodic shear deformation and steady flow on a typical amorphous polymer is discussed. Forced sinusoidal vibrations were applied and the complex viscosity was determined. The action of a vibration of finite amplitude is equivalent to steady flow with a definite finite shear rate. Both processes cause truncation of the long-time part of the relaxation specturm. It may be accepted to a first approximation that the long-time boundary of the remaining part of the relaxation spectrum conforms to the long-time part of the initial spectrum, even if the plateau region of the spectrum is truncated. The concept of limiting truncation of the short-time part of the spectrum is introduced, this corresponding to the minimum absolute value of the complex viscosity versus reduced frequency and the lowest values of the dynamic and apparent viscosities. With an approximate representation of the relaxation spectrum, calculations were made of the maximum values of the viscosity and the coefficient relating the first difference of normal stresses to the square of the shear rate, and also of the apparent viscosity and normal stresses as functions of the shear rate. The calculated values are compared with experimental measurements, and it is shown that the correlation of the apparent viscosity and the absolute value of the complex viscosity is distributed at high frequencies, being superseded by a correlation between the apparent and dynamic viscosities.
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  • 169
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1323-1336 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular orientation in poly(ethylene terephthalate) (PET) fibers was studied by polarized fluorescence. The observed amorphous orientation of the spun as fiber was not random but uniaxial along the fiber axis. This orientation increased with draw ratio up to about 2 and then remained fairly constant. The amorphous regions of PET fibers were disoriented when the fibers were heated while unconstrained. The fluorescence data obtained were correlated with shrinkage measurements. Fluorescence data indicated that spin drawing had more effect upon orientation than subsequent drawing of the fiber, whereas birefringence data indicated the opposite. The reason for this behavior is discussed.
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  • 170
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The recently developed methods of characterizing branching in polymers from gelpermeation chromatography and intrinsic viscosity data are verified experimentally. An iterative computer program was written to calculate the degree of branching in whole polymers. Long-chain branching in several low-density polyethylene samples was determined by both the fraction and whole polymer methods. The two methods gave consistent ranking of the branching in the samples although absolute branching indices differed. Effects of various experimental errors and the particular model used for branching were investigated. For polyethylene, the data show that the effect of branching on intrinsic viscosity is best described by the relation 〈g3〉W1/2 = [η]br/[η]1 where 〈g3〉w is the weight-average ratio of mean-square molecular radii of gyration of linear and trifunctionally branched polymers of the same weight-average molecular weight.
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  • 171
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1413-1414 
    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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  • 172
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1491-1502 
    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 optical rotation of the environment is calculated for the Hv and Vv low-angle light-scattering patterns of two-dimensional spherulites. As with the effect or birefringence, the change in the Hv pattern is greater than that of the Vv pattern. With increasing optical rotation, the patterns lose their characteristic shape and become more circular.
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  • 173
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1521-1543 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The processes associated with the deformation and fracture of polystyrene tested in uniaxial tension have been studied over a range of strain rates from 1.4 × 10-2 to 4.3 × 10-7 sec-1 and at constant stresses between 4.1 and 2.9 kg/mm2. The effect of strain rate on the surface craze distribution prior to fracture, the fracture stress, the mechanism of nucleation of cracks, and the nature of fracture surfaces associated with slow and fast crack propagation have been determined. The changes in fracture surface appearance have been studied using optical and stereoscan microscopy. The observations are consistent with the model presented in a previous paper. Fracture is preceded by craze formation, cavitation in the craze, coalescence of cavities to form large planar cavities which propagate slowly until a critical stage is reached at which fast crack propagation occurs. The effect of changes of strain rate and material variables on these processes is discussed.
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  • 174
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1585-1597 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to study the dielectric behavior of polyoxymethylene prepared by radiation-induced solid-state polymerization, large crystals of tetraoxymethylene (2 cm in diameter) were prepared by Bridgman's method and polymerized by γ-rays. The x-ray diffraction pattern of the polymer did not reveal the existence of a so-called amorphous region. In dielectric measurements, only one dielectric absorption was observed in the low-temperature region, while in the high-temperature region ε″ did not change up to about 120°C, where thermal decomposition started. When the specimen was stabilized by acetylating the endgroups in the solid state, ε″ did not change up to about 150°C. This dielectric absorption showed a significant anisotropy for the direction of an applied field. The dielectric absorption was much larger when the electric field was perpendicular to the fiber axis than when the field was parallel. The dielectric absorption was larger in a specimen which was estimated to be more imperfect according to DSC analysis. This leads to the conclusion that the dielectric absorption is attributable to defect regions. On the other hand, the dielectric absorption became larger with increasing numbers of terminal OH groups, and hence it is attributable to the response of the terminal OH groups. Moreover, the dielectric absorption was depressed by the acetylation of the OH groups in the solid state. It is, therefore, concluded that the dielectric absorption observed in polyoxymethylene prepared by solid-state polymerization of tetraoxymethylene is due to the response of terminal OH groups localized in defect regions. Polyoxymethylene crystallized from the melt gives an asymmetric low-temperature absorption. This asymmetry can be ascribed to the superposition of two relaxation processes. When its absorption curve is compared with that of the solid-state polymerized polymer, the low-temperature component can be assigned to crystal defects and the high temperature one to amorphous regions.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1637-1637 
    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 8 (1970), S. 1651-1659 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is pointed out that a theory proposed by Vrij for the expansion of a linear polymer chain in solution beyond its unperturbed size is also applicable formally to branched chains. The theory predicts the temperature at which the chain obeys random-flight statistics to be lower for a branched chain than for a linear one (for a polymer-solvent system exhibiting the usual upper critical consolute point). Vrij's derivation follows a well-known procedure of Flory, but refines it to take account of the variation of the time-averaged segment density with distance from the center of mass of the chain. This modification in combination with a somewhat different derivation is shown to lead to a similar result. Yet another scheme for “correcting” Flory's theory is outlined. Some reasons are advanced for questioning the physical significance of these small modifications of Flory's theory, all of which depend on the retention of previously ignored terms in power series expansions.
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  • 177
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1713-1722 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical and optical properties of a polyester-styrene copolymer have been investigated by means of drop tests at strain rates from 38 to 113 sec-1 for strains less than 50%. Over this range of rates, the optical behavior was found to be linear with strain and independent of strain rate while the elastic-plastic mechanical behavior was only slightly dependent on strain rate. Comparison with the results of similar experiments at lower strain rates achieved by means of an Instron tester reveals that both mechanical and optical properties vary significantly with strain rate. The variation of flow stress with strain rate was found to obey a power law.
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  • 178
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1741-1754 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hyperelectronic polarization is a molecular mechanism which can produce very large dielectric constants in certain macromolecular solids. The present paper reports studies of the frequency, pressure, and temperature responses of this extreme polarization and related electronic conductivity on a variety of new polymers. The polymers studied were quinazone, metallo-organic dithiooxamide type, and pyropolymers. The latter were examined in pure and in metal-doped forms. Dielectric constants ranging from 10 to 500 were observed for the quinazone polymer, which was, incidentally, found to exist in two forms. Dielectric constants ranged from 30 to 100 for the metallo-organic polymer from 25 to 10,000 for the pure pyropolymer and were of the order of 500 for a calcium doped pyropolymer. One set of nickel-doped pyropolymers was found to conduct quite well (resistivity 76.8 × 10-6 ohm-cm).
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  • 179
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1841-1844 
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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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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1879-1883 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamics of deformation of ethylene-propylene copolymer crosslinked by dicumyl peroxide with addition of sulfur or maleic anhydride has been studied. Both the entropic (fS) and energetic (fU) components have been studied at elongations α up to 65%. It was found that the course of fU/f, where f is equilibrium stress, in dependence on α agrees with the determined difference in both chemical and physical bonds.
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  • 181
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1865-1877 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawing of mats of linear polyethylene single crystals prepared from dilute solution is possible at temperatures above about 90°C. The structure and properties of the drawn specimens are much different from those ordinary drawn bulk polymer. Drawn mats have been investigated by differential scanning calorimetry. The characteristic experimental results are: (a) a broad melting curve, (b) considerable superheating depending on the rate of heating, (c) constancy of the melting point and the heat of fusion with annealing, (d) deviation from the relation between the heat of fusion and the density obtained for the drawn bulk specimens, (e) appearance of two melting peaks in samples annealed at temperatures above about 130°C. These results imply that the structure of the drawn mat is characterized by a larger number of the tie chains connecting the neighboring crystals (the structure postulated in earlier papers) than is the case in ordinary drawn bulk polymer. It can be concluded that the transformation of a fringed micellar type of structure to the folded lamellar structure may be difficult during annealing unless crystals melt and then recrystallize during cooling.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1955-1969 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are developed for describing the effect of interspherulitic interference on the scattering of light by anisotropic spherulites. These are used to account for the variation in VV and HH scattered intensity during the course of spherulitic crystallization. The scattering depends upon the number of spherulites, their size, their anisotropy, the difference between one of their polarizabilities and that of the surroundings, and the radial distribution function of spherulite centers.
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  • 183
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 35-45 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for the determination of the molecular weight spread in the narrow peaks in the GPC chromatograms of nitric acid-degraded polyethylene is presented. It is found that polar endgroups added to the polymer chains during scission cause the peaks to be broader than those of paraffins with the same molecular weight spread. After allowing for this extra instrumental broadening, estimates are made of the molecular weight spread for unannealed and annealed single crystals of polyethylene and bulk polyethylene as a function of degradation time. It is proposed that after long degradation times the molecular weight spread is a measure of fluctuations in the original crystalline lamellar thickness.
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  • 184
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of several toluene-soluble polymers at the toluene-water interface has been investigated by using the duNouy ring method of measuring interfacial tension γT/W. Polystyrene and poly(ethylene-co-vinyl acetate) (11.1 mole-% vinyl acetate) have little affinity for this interface at 29°C, but poly(methyl methacrylate) (PMMA) (M̄n = 420,000) and ethyl cellulose (EC) (M̄n = 50,100; 49.1% ethoxyl) adsorb significantly at concentrations as low as 1.0 × 10-4 g/100ml. A plot of interfacial tension lowering versus initial logarithm of initial bulk phase polymer concentration is linear from 1.0 × 10-4 to 1.0 × 10-1 g/100 ml for EC and 1.0 × 10-4 to 1.0 × 10-2 g/100 ml for PMMA. When the PMMA concentration increases to 1.15 × 10-1 g/100 ml, its adsorption behavior changes markedly. Prolonged time effects occur and adsorption becomes dependent upon dissolved water content of the toluene prior to formation of the toluene/water interface. Such effects are not observed with the other solutions studied. Increasing temperatures have variable effects on values of γT/W for the polymer solutions studied. Experiments with various polymer mixtures indicate that the polymer lowering T/W the most is preferentially adsorbed at the toluene-water interface and rapidly displaces less strongly adsorbed polymers.
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  • 185
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 127-141 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The investigation of the effect of molecular structural variables on the melt viscosity of polyethylene was extended to the shear dependent region by application of a reduced variables treatment following, in a formal sense, that of Bueche. Viscosity-shear rate data were obtained for a series of experimentally polymerized linear polyethylene samples having a range of molecular weights and molecular weight distributions as characterized primarily by gel permeation chromatography. These data could be superimposed on a single reduced variables flow curve using parameters which were a function only of temperature, limiting Newtonian viscosity, M̄w, and M̄w/M̄n. The same treatment was successfully applied also to branched (low-density) fraction data discussed in a previous paper, with additional correction for long-chain branching. However, different reduced variables curves were obtained for the branched and linear cases.
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  • 186
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 173-174 
    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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  • 187
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 191-205 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements have been made on a series of linear atactic polystyrenes whose molecular weights range from 900 to 1.8 × 106, where Mw/Mn ≪ 1.2. Spin lattice relaxation times have been measured in the laboratory frame (T1) and in the rotating frame (T1ρ) in the temperature range 90-500°K. Two major relaxation minima were observed in both sets of measurements. The high temperature process corresponds to the glass transition (α process), the position of the minimum depending on the chain length. The low temperature process appears to originate from the n-butyl endgroups in the polymer, its position being independent of chain length while its intensity is inversely proportional to molecular weight. No other minima were observed, in contrast to some other observations made by broadline and pulsed NMR techniques. Relaxation was exponential in all cases except in the region of the high temperature T1ρ minimum and above. This nonexponential behavior is possibly connected with the transition at T 〉 Tg observed by a number of other techniques and which is thought to correspond to a transition between two types of liquid state. A correlation frequency diagram has been drawn for all the processes observed in polystyrene by other techniques, (α, β, αβ, γ, and δ) which shows that the T1 and T1ρ minimum positions correlate well with the α process and that there is a possible contribution to the relaxation due to the γ process on the low temperature side of the α process. At these measurement frequencies the α and β processes are merged into an αβ process. There is no evidence for a contribution from the mechanical δ process. The effect of the endgroups is observed to very high molecular weights (4.98 × 105), and it seems that a three-dimensional diffusion model would be more adequate than the one-dimensional model used to interpret similar behavior of paraffins and polyethylenes. Measurements of T1 in the low-temperature region would constitute a method for a rough measurement of the molecular weight of these polymers.
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  • 188
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 225-242 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calorimetric and dilatometric studies have been made of the fusion process of linear polyethylene crystals precipitated by high speed stirring from solution. It is shown that long-time annealing at elevated temperatures alleviates the superheating observed when rapid heating rates are employed. By the annealing procedures that have been adopted, a small but demonstrable fraction of high melting material can be produced whose melting temperature depends on the crystallization temperature. For crystallization at 105°C, followed by annealing at 142°C, a melting temperature of 146.0 ± 0.5°C is observed. The dissolution temperature in xylene, determined for the same sample, is consistent with the high melting temperature observed for the pure polymer. It is recognized that a state of high axial orientation need not necessarily be identified with extended chain crystals. Consequently, the increased melting temperature can result from either an increase in the crystallite size or a reduced interfacial free energy relative to crystallites produced by the more conventional mode of crystallization.
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  • 189
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 289-294 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear dependence of the intrinsic viscosity and the conformation of high molecular weight polyisobutylene in dilute solutions of decahydronaphthalene under shear were determined simultaneously. Experimental variables investigated were the shear rate (0 to 2 × 103 sec-1), the molecular weight (1.0 × 107 to 1.7 × 107) and the polymer concentration (1.8 × 10-4 to 8.4 × 10-4 g/cc). Correlations allowing concentration and shear rate normalization for any one sample are described. Conformational extention ratios along the orientation direction of the deformed molecule to 1.42 and intrinsic viscosity ratios (sheared to zero shear) to 0.5 were observed.
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  • 190
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 317-318 
    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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  • 191
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 355-369 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties and structures of polyethylene films drawn from mats of single crystals were investigated in comparison with films drawn from bulk polymer. The most important result obtained is that the structural reorganization stimulated by mechanical stress and annealing occurs with much greater difficulty in the mat-drawn film. The chief mechanical characteristics of the film are a very low extensibility and a very high modulus. Structural characteristics, such as the double-orientation of the crystalline region and the morphology of the crystals, do suffer no substantial changes during annealing at high temperatures. This stability of the structure can be related to the characteristic fine structure of the mat-drawn film in which there are a much larger number of tie chains, connecting neighboring crystals, than in the bulk-drawn specimen. Relaxation of the amorphous region and a notable increase in long spacing take place in the mat-drawn sample as in ordinary bulk-drawn samples. However, the morphological changes of the crystals accompanied by the folding back of chains seem to take place with great difficulty during annealing even in the vicinity of the melting point.
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  • 192
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 417-436 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique for estimating Mc, the molecular weight between crosslinks, of amine-cured epoxy resins is described. The technique is based upon the stoichiometry of the curing reaction and the amount of primary amino and epoxy groups remaining in the polymer at a given time. The Mc values so calculated are shown to be consistent with Mc results obtained from separate measurements of swelling and the polymer-solvent interaction parameter χ1 for the range of polymer concentration in which both measurements could be obtained. A means of estimating the relative reaction rates of the primary and secondary amino groups with the epoxy groups is given. Under proper curing conditions the amine-epoxy reaction goes very nearly to completion. The presence or absence of an exotherm has no noticeable effect on the course of the reaction between bisphenol A-epichlorohydrin (Epon 828) and methylene dianiline.
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  • 193
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 447-453 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two types of (KPO3)n crystals have been obtained: transparent crystals and semitransparent crystals that grew in the neighborhood of the wall of the crucible. In the latter type of crystals, four kinds of radicals, denoted B, C, D, and E, are observed by ESR measurements at 77°K on crystals irradiated with γ-rays at the same temperature. The probable structure of B, C, and D radicals is concluded to be —O—PO̊2—O— from their g values and hyperfine constants (the superscript circle indicates a hole trapped in the radical). When these crystals are heated to room temperature, the ESR spectra of B, C, and D radicals disappear and the spectrum of another radical appears. This radical, designated A, has the possible structure —O—ṖO2. The assumption that B radicals thermally decompose into A radicals is confirmed by experiment. With the transparent crystals, C, D, and E radicals are observed at low temperature, but only E radicals are stable at room temperature. The structure of the E radical is thought to be\documentclass{article}\pagestyle{empty}\begin{document}${\rm \hbox{---}O \hbox{---}PO}_2{{_\circ} \atop ^{\hbox{---}}} {\rm PO}_2 {\rm \hbox{---}O\hbox{---}} $\end{document}, but more detailed studies are required.
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  • 194
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 167-172 
    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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  • 195
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 513-518 
    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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  • 196
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 817-832 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface potentials of monolayers of poly(methacrylic acid) (PMA) have been studied as a function of the pH of the subsolution. The influence of the macromolecular configuration on the properties of the ionizable groups was more particularly investigated. Orientation of molecules in the monolayer may be imposed by the stereoregularity of PMA (isotactic, atactic) and by the nature of the interface (air-water, cyclohexane-water). The results are analyzed in terms of theories of the ionic double layer (Gouy model, Donnan equilibrium) which permit the determination of the degree of ionization α of the film. The value of α gives indications about the orientation of specific groups of the macromolecular chain, i.e., of the ionized monomer units. Indeed, at the air-water interface, the film of isotactic PMA is more acid than that of the atactic sample, and at the cyclohexane-water interface, the degree of ionization is greater than at the air-water interface. These properties are the consequence of a modification of orientation of the hydrophilic groups with respect to the aqueous phase as a function of the stereoregularity of the sample and the nature of the interface. The variation of α with the pH of the substrate phase may be used to calculate an intrinsic dissociation constant Ks° of the molecules in the film. The value of Ks° is not modified by spreading conditions and remains very similar to that obtained in solution.
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  • 197
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 161-165 
    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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  • 198
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 177-190 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational properties of optically active macromolecules are considered. A statistical zigzag model is used for the calculation of averaged physical properties. The macromolecule is considered to consist of segments of two different types with a statistical distribution of lengths. The expressions for the mean square of the end-to-end vector h2 and the dipole moment μ2 and also of the mean optical anisotropy ΔA and the anisotropy of the optical rotation tensor ΔG were obtained in the cases of freely jointed and freely rotating segments. The equations obtained were applied to the problem of the helix-coil transition. In the case of poly-α-olefins the values of h2, μ2, and ΔA, are larger than corresponding values for typical optically inactive macromolecules. The anisotropies ΔA and ΔG of two poly-α-olefins of similar structures were calculated. The polarizability theory of optical activity was used for the calculations of ΔG. The values obtained for ΔA are similar, but the values of ΔG differ markedly. The possibility of obtaining valuable information about the structure of optically active macromolecules in solution by a study of anisotropy of the optical rotation tensor is considered.
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  • 199
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 243-276 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray diffraction method for the simultaneous determination of crystallinity (including intracrystalline defects), effective Debye-Waller factors, and atomic positions has been developed and applied to semicrystalline polyethylene. It was found that this material unambiguously constitutes a two-phase system. Measurements of intracrystalline lattice disorder in the chain direction and perpendicular to the chain direction show these to be in the ratio 1:2.5. Lattice disorder was principally of the first kind. Paracrystalline disorder in the [110] direction was less than 2.4% at all experimental conditions. Results include measurements of degree of crystallinity, particle size, space group, and unit cell parameters and variation of these quantities with crystallization temperature, ambient temperature, and time.
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  • 200
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 311-316 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 7 Ill.
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