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  • 1995-1999
  • 1970-1974  (872)
  • 1970  (872)
  • Physics  (526)
  • Analytical Chemistry and Spectroscopy  (346)
  • Nuclear reactions
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Years
  • 1995-1999
  • 1970-1974  (872)
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 19-34 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that dicarboxylic acids of uniform lengths, obtained by degrading chain-folded polyethylene single crystals, can be converted to paraffins via the intermediate diiodide by means of the procedure of Barton et al. Thus we are now in the position of obtaining uniform paraffins of chain lengths longer than hitherto available for the study of the crystallization of oligomeric chains. Measurements of melting points and heats of fusion revealed major differences between the paraffins and the corresponding parent dicarboxylic acids. It follows that such measurements on the unmodified products of the nitric acid degradation cannot be used directly for the assessment of the chain traverse length and the degree of crystallinity. It was found further, that the intermediate diiodide is a sufficiently close approximation to the paraffin for the purposes just quoted.
    Additional Material: 9 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 89-103 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical justification for using M[η], or a similar quantity, as a universal calibration parameter in GPC is reviewed. The equation based on this parameter is applied to transform the primary calibration curve, obtained by means of polystyrene samples, into calibration curves for poly-α-methylstyrene, polypropylene, and linear polyethylene. The Mark-Houwink equations for these polymers, as they are used in the transformation, are discussed. The resulting GPC calibration curves are compared with molecular weights and peak elution volumes of fractionated poly-α-methylstyrene and polypropylene. The same comparison is made with samples of polypropylene and polyethylene having very broad molecular weight distributions. The agreement lies within experimental error.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 148-152 
    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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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 482-482 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 207-224 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A discussion is given of the behavior of a mathematical model chosen to approximate conditions during precipitation chromatographic fractionation of polymer (Baker Williams fractionation). With only one molecular weight species of polymer a complete solution of the mathematical model was obtained. With more than one species it was necessary to use a computer solution. Curves showing the movement of polymer containing one and two species of polymer are given for a variety of conditions of operation. It was found that the degree of fractionation of polymer approaches a limiting value with increasing length of column. Under some conditions the degree of fractionation may go through a maximum with length of column. The equilibrating distance (distance of travel of the liquid phase required to establish equilibrium of polymer between the liquid and the bed) was found to be very important in determining the fractionation.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 277-287 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies have been made on the dynamic and steady-shear melt rheology of an ethylene-methacrylic acid copolymer and two of its salts obtained by partial neutralization with sodium and with calcium bases. Measurements were made with a Weissenberg rheogoniometer over a broad range of shear rates and frequency in the temperature interval mainly from 100 to 160°C. The temperature coefficients of dynamic and steady shear viscosity are evaluated at both constant shear rate and constant stress. Likewise, complex dynamic viscosities and apparent high steady-flow viscosities and intercompared at equivalent frequencies and shear rates. The un-ionized acid copolymer shows good correlation between the frequency dependence of the complex viscosity and the shear rate dependence of the apparent viscosity. This is not true for either the sodium salt or the calcium salt. These results are consistent with the two-phase structural model for these materials, i.e., a matrix of hydrocarbon in which are embedded ionic domains.
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 305-310 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enchanced low-shear melt viscosity of branched polybutadienes is shown to be sensitive to dilution with low molecular compounds. The viscosity of branched polymers falls more rapidly with dilution than that of linear polymers, i.e., branched polymers show increased response to plasticization. At least one instance is demonstrated in which the viscosity ratio ηbr/ηlin reverses from a value greater than unity to less than one in passing from dry polymer to rubber extended with relatively large quantities of oil.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 371-381 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Normal stress and shear stress of concentrated polystyrene solutions in a chlorinated diphenyl were measured under steady flow and oscillatory shear flow in a Weissenberg rheogoniometer. The normal stress difference was observed to oscillate at double the frequency of the applied shear strain with amplitude proportional to the square of the applied amplitude, while the shear stress was found to oscillate at the same frequency with amplitude proportional to the applied amplitude. A theoretical relation between the displacement of the oscillatory normal stress difference from zero level and the dynamic modulus derived by Lodge and other investigators was confirmed experimentally, and the theoretical predictions of Coleman and Markovitz concerning the relation among steady-flow normal stress difference and dynamic modulus were also confirmed. However, the theoretical predictions of Lodge, of Spriggs, Huppler and Bird, and of Williams on the relation between the amplitude and phase of oscillatory normal stress and those of oscillatory shear stress did not agree with experimental results.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 47-59 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method of preparing thin uniform films of high polymers has been examined for growing single crystals from solution. Single crystals of polyethylene, polypropylene, polybutene-1, polyacrylonitrile, and cellulose triacetate have been obtained by this method. Different stages of growth reveal different growth features that are also obtained from solutions of these polymers by changing temperature and concentration.
    Additional Material: 19 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 81-87 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The high degree of flexibility of blends containing minor amounts of partly crystalline copolymers of ethylene and vinyl acetate in paraffin wax seems to be a manifestation of some type of interaction. Low-angle x-ray diffraction of such blends showed a new long spacing intermediate in length between the polymer long spacing and the c axis length of the wax unit cell. This new long spacing appears to be a consequence of isomorphism involving cocrystallization of polymeric ethylene sequences and wax molecules. A lesser type of isomorphic interaction, epitaxy, occurs in polyethylene-wax blends: wax overgrows crystals of already crystallized polyethylene in the same orientation without a change in its c axial dimension.
    Additional Material: 2 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 143-147 
    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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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 893-901 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have derived from the Eyring theory of non-Newtonian flow a yield condition which is valid for an arbitrary state of stress. Experimental data obtained in simple axial compression tests show the influence of the hydrostatic stress on the yielding of poly(vinyl chloride). This fact confirms the proposed condition and disproves the von Mises criterion. Tension-torsion tests performed on thin tubes lead to results which fit our condition fairly well. The pattern of Lüders' lines appearing on the surface of thin tubes subjected to simple tension, simple shear, and tension-torsion are parallel to the direction where the value of the normal stress is equal to the hydrostatic stress.
    Additional Material: 8 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 957-967 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.
    Additional Material: 6 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 999-1010 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the internal motion in organosilicon polymers by wideline nuclear magnetic resonance has been extended to a pair of dimethylpolysilazanes crosslinked through trifunctional silicon. The data suggest that there is considerable internal motion in all silazanes at 77°K. Evidence is presented for the presence of C3 rotation of the methyl groups, as well as rotation or torsional oscillation of the Si(CH3)2 groups about the polymer backbone. Upon warming the NMR line is seen to narrow, and this is associated with the onset of additional motion, including chain translation and chain flexing or bending. Crosslinking through silicon increases the barrier to chain translation while decreasing the barrier to chain flexing or bending.
    Additional Material: 5 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1027-1037 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-2,5-distyrylpyrazine (poly-DSP) was investigated by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and measurements of dynamic viscoelastic and electrical properties. From DTA and TGA studies it was confirmed that poly-DSP melts at 321°C and depolymerizes rapidly to the monomer at temperatures between 335°C and 345°C in helium. The polymer is affected by oxygen above 200°C. The E′ value from dynamic viscoelasticity measurements on amorphous film is 2 × 1011 dyne/cm2 at room temperature. It decrease abruptly in the temperature range 140-150°C; but the net decrease of E′ within this temperature range is relatively small. The electrical properties of amorphous poly-DSP are characterized by a small temperature dependence of the dielectric constant between room temperature and 100°C. The dielectric loss tangent was observed to be small, and the dc conductivity was extremely small. It is concluded that rotation of the phenyl branches in the polymer occurs above -30°C and the glass transition occurs at about 150°C. These properties are discussed in some detail in relation to the polymer structure.
    Additional Material: 11 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1111-1126 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Comonomer and stereosequence distributions in linear high polymers are considered from the point of view of the general theory of stationary random sequences. Although the discussion is centered about binary polymerizations which may be regarded as stationary Markov processes of low order, attention is paid to distinguish results valid for any stationary random process including stationary non-Markov processes from those special to a particular Markov process. Alternative derivations of copolymer composition equations are given along with a corrected version of a previously suggested scheme of relating conditional probabilities of different orders. The nature and relative merits of the several measures proposed in the literature to characterize comonomer and stereosequence distributions are also discussed in some detail.
    Additional Material: 2 Tab.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1177-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(vinylidene fluoride) is affected by orientation and crystal modification. The loss peak caused by molecular motion of the molecules in crystalline regions appears at about 70°C (110 Hz) (α1 absorption) for the α form, and at about 110°C (110 Hz) (α2 absorption) for the β form. Orientation significantly affects the magnitude of the β absorption which appears at about -40°C. The very high value of the dielectric constant for stretched film is believed to be due to the orientation effect. The γ absorption, which is assumed to be local-mode absorption, is not so much affected by orientation. An additional loss peak has been found at around 0°C in dynamic mechanical measurements, but the molecular mechanism is unknown.
    Additional Material: 6 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 467-479 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic method for investigating the mechanism of permeation and diffusion through polymers has been explored. The permeation cell consists of two compartments separated by the membrane. The permeant (gas, vapor, or liquid) is introduced into one compartment; a carrier gas (helium) flows at constant rate through the other and sweeps the permeant which diffuses through the membrane to the thermal conductivity detector. Both compartments are at atmospheric pressure; thus no or little membrane support is required, and leakage problems are minimal. Moreover, the same membrane can be used over a wide temperature range and for diverse permeants. The detector signal is at any instant proportional to the permeation rate. A simple mathematical formalism for deriving the diffusion coefficient from the transient permeation rates has been developed. The measured diffusion and permeability coefficients of CO2, O2, and N2 through low-density polyethylene closely agree with literature values. Permeation of hexane and benzene through polyethylene follows a complex diffusion law, and the rate depends on the thermal history of the system. The dynamic method is particularly suited to the study of transitions in polymers. Changes in permeation rates, usually occurring at transition points, can easily be discovered by slow temperature scanning of the system.
    Additional Material: 7 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 487-487 
    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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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 519-528 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three transitions are detected dilatometrically when partially isotactic poly(propylene oxide) melts. One transition, the temperature of which is independent of the crystallization temperature over a wide range below 60°C, is ascribed to the melting of lamellar crystallites which are limited in thickness by the average isotactic sequence length alone. The other two transitions, the temperatures of which vary with the crystallization temperature, are ascribed to the melting of lamellar crystallites with thickness determined predominantly by three- and two-dimensional primary nucleation acts. The theory of Flory is adapted and applied quantitatively to the melting points of three crystalline fractions of poly(propylene oxide), obtained from a polymer produced via the zinc diethyl and water catalyst system. This method leads to a thermodynamic melting point of isotactic poly(propylene oxide) near 82°C.
    Additional Material: 3 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 583-594 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic markings of concentric bands are formed on the fracture surface of tensile specimens under certain loading conditions. The marking form in the fast crack growth region of the mirror area of fracture. Optical and electron optical microscope techniques have been used to study the morphology of the markings. It is shown that in this region the crack propagates along the interface between the craze, in which the crack nucleated, and the bulk material. The mackerel pattern is caused by the crack jumping from one craze-matrix interface to the other.
    Additional Material: 13 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 605-624 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Incorporation of plasticizers or other inert, liquid diluents causes a profound weakening of rubbers. The modulus of elasticity and tensile strength decrease approximately with the square of the gel fraction v0 of rubber which was present at the time of formation of the three-dimensional network. Equlibrium swelling of plasticized rubbers is well represented by v2m = kv0, where v2m is the volume fraction of rubber network in the swollen state, at equlibrium, and k a constant equal to v2m for the unplasticized rubber. This swelling law is independent of the way in which v0 is obtained; inert liquid diluents, comprising molecularly dispersed compounds, as well as suspensions of insoluble liquids, gases, and chemically inert, solid fillers yield the same relation. Further, it is independent of the chemical nature of solvent and rubber. It appears that also the mechanical properties of foams, liquid-filled foams, and plasticized elastomers containing the same volume fraction of network rubber are very similar.
    Additional Material: 7 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 649-652 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 657-678 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On axial extension of polymer melts at constant deformation rates, the development of high-elastic deformation is of predominant importance during the initial period. High-elastic deformation is accompanied by a rise in viscosity and in the modulus of high-elasticity and by retardation of the relaxation processes in the region of large relaxation times. At relatively low deformation rates, the rise in viscosity and high-elasticity modulus and the retardation of relaxation processes may give way to a decrease in viscosity and high-elasticity modulus and acceleration of relaxation processes, so that stationary flow regimes are attained. The transition from strain regimes with increasing viscosity and modulus of high elasticity to those with a decrease of these quantities corresponds to an increase in the rate of accumulation of irreversible deformation. Accordingly, a competing influence due to the orientation effect and to destruction of the network of intermolecular bonds becomes evident while stationary flow is being attained. The orientation effect must be responsible for the retardation of the relaxation processes, whereas rupture of the intermolecular network bonds results in structural relaxation accelerating relaxation processes. In contrast to shearing, during extension the orientation effect is of predominant importance. Hence in stationary flow regimes the viscosity may not only remain independent of the rate of strain, but even increase with it. In this case the contribution of the large relaxation times to the relaxation spectrum increases with increasing stress in stationary flow regimes. The fact that the longitudinal viscosity and the modulus of high elasticity are independent of the stress in stationary flow regimes does not guarantee linearity of the mechanical properties of the polymer in the prestationary stage of deformation when complex changes occur in its relaxation characteristics. At high deformation rates the viscosity and the modulus of high elasticity keep rising with increasing deformation until rupture occurs. Determination of the strength of polystyrene samples vitrified after extension showed that it is due not to the entire degree of extension, but only to the value of accumulated high-elastic deformation. The strength of the vitrified samples is to a first approximation independent of the rate at which the melt was extended.
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  • 25
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 727-738 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation data have been obtained for two ethylene-methacrylic acid copolymers (containing about 4 mole-% methacrylic acid units and about 8 mole-% methacrylic acid units, respectively) and the lithium, sodium, and calcium salts prepared by partial neutralization of the polyacids. The frequency range employed was from 50 Hz to 10 kHz and the temperature range was from -130°C to 100°C. Attention is focused on three dielectric loss regions labeled β, β and α in order of increasing temperature. The β′ process (-10°C at 100 Hz in the salts only) correlates with a mechanical loss process previously reported and is attributed to microbrownian motion taking place in an amorphous hydrocarbon phase. The β′ process (20°C at 100 Hz) has also been observed mechanically and is attributed to the same mechanism as the β process. The higher temperature of this relaxation compared to the β relaxation is attributed to the presence of acid groups which form crosslinks composed of interchain hydrogen bonds. The α process (〉50°C at 100 Hz in the salts only) correlates with dielectric and NMR data previously reported for a sodium salt and is assigned to motions within ionic domains formed by the clustering of salt groups.
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  • 26
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 807-811 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 27
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 815-816 
    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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  • 28
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sedimentation equilibrium in the ultracentrifuge means that there is such a distribution of molecular species throughout the cell, that the centrifugal forces are balanced by differences in the activities. This provides a method for determination of the activities and the chemical potentials in polymer solutions which, in principle, is very simple and reliable. A complication is caused by polydispersity of the dissolved polymer. If one assumes that the interaction parameter depends on concentration and temperature, but not on molecular weight, it is possible to determine the chemical potential of polymer and solvent from the ultracentrifugal data. Experiments have been carried out on the systems polystyrene-toluene and polystyrene-cyclohexane at different temperatures and in the concentration range 0-80 wt-%. The results are expressed in the data for the chemical potential of the solvent, the number average chemical potential of the polymer and the interaction parameter χ.
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  • 29
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 921-935 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several partially interpenetrating polymeric networks (IPN) were made by combining chemically different linear elastomers. The polymer combinations were deposited as films from aqueous emulsions made by mixing the individual emulsions in equal proportions. The films were crosslinked to form two superimposed networks. In two cases, the networks were cleanly separated by hydrolysis of one of the component networks to demonstrate that there was no chemical interaction between the polymers. Measurement of crosslink density showed that, in most cases, partial interpenetration does occur as evidenced by an effective crosslink density of the IPN's greater than the arithmetic mean of the crosslink densities of the component networks. The swelling ratios, densities, and stress-strain properties were determined. For one of the network combinations, a poly(urethane-urea) and a poly(butadiene-acrylonitrile), a series of IPN's varying in polymer composition was made. The swelling ratios and densities are close to the arithmetic means; however, both the tensile strength and crosslink density exhibit a maximum at about 70% poly(butadiene-acrylonitrile). The maximum tensile strength is actually significantly higher than that of either of the component polymers. The elongations all approach that of the poly(urethane-urea), the more extensible material, except for compositions approaching 100% poly(butadiene-acrylonitrile), which exhibit a very low extensibility.
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  • 30
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 969-977 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic wide-line proton magnetic resonance absorption spectra of a number of representative cellulose preparations have been obtained in the dry state and after addition of about 7% water. Line widths, second moments, spin-spin and spin-lattice relaxation times have been determined. The second moment of the absorption curve of dry cellulose was found to correlate well with the crystalline fraction for most specimens. A technique is described for determining the number of water-cellulose protons exchanging relative to the number of cellulose protons not exchanging. The reduction in absorption line width observed when water is added to cellulose is shown to be quantitatively consistent with such a proton exchange phenomenon.
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  • 31
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1755-1772 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of selenium has been studied in light of present concepts of crystallinity in crystalline organic polymers. Spherulitic crystallization and resultant morphology were examined as a function of temperature by transmission and replication electron microscopy, electron diffraction, and optical microscopy. Evidence is given for polymer chain folding during crystallization of trigonal selenium. Theoretical thermodynamic calculations presented yield several thermodynamic values including an equilibrium melting point of 219.2°C, a fold surface energy of 337 ergs/cm2 and a lateral surface energy of 9.8 ergs/cm2.
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  • 32
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1803-1821 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various procedures for universal calibration in gel-permeation chromatography with polystyrene gels are examined for polystyrene and polydimethylsiloxane fractions. For o-dichlorobenzene at 138°C, experimental intrinsic viscosity-molecular weight data show that the Mark-Houwink exponents are 0.70 and 0.57 for polystyrene and polydimethylsiloxane, respectively. In principle, this difference permits a distinction between the various polymer size parameters proposed for universal calibration. An interpretation of the experimental polydimethylsiloxane calibration for o-dichlorobenzene at 138°C requires a consideration of errors in average molecular weights and errors arising from the use of average molecular weight instead of peak molecular weight. When calibration procedures utilizing hydrodynamic volume and unperturbed dimensions are examined, the difference between them is comparable with experimental error. If the Flory-Fox viscosity expression is employed, the perturbed end-to-end distance (or radius of gyration) and the hydrodynamic volume give equivalent universal calibrations. The experimental data are sufficiently accurate to show that the perturbed dimension determined with the Ptitsyn-Eizner relation does not give an adequate universal calibration.
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  • 33
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1545-1564 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization of compression-molded isotactic polypropylene and polyethylene is invariably spherulitic; generally, nucleation occurs randomly throughout the sample. In a special case where nucleation predominates at the surface, spherulitic growth centers become crowded and are forced to propagate unidirectionally into the bulk (transcrystallinity). Conditions for the formation of transcrystallinity have been investigated by optical and scanning electron microscopy. The occurrence of transcrystallinity is attributed to heterogeneous nucleation induced at the mold surface. To be effective, the mold surface must have a nucleating efficiency equal to or greater than that of adventitious nuclei present in the polymer. As the crystallization temperature approaches the melting point, the activity of mold surfaces is found to increase leading invariably to transcrystalline formation. The degree of activity of various mold surfaces correlates with the known activity of specific dispersed nucleating agents having similar chemical structures. Contrary to claims in the literature, the surface energy of the mold surface and temperature gradients across the melt surface do not play a primary role in transcrystalline formation of polypropylene.
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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1909-1916 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow behavior of α,ω-dihydroxypolydimethylsiloxanes, having a weight-average number-average molecular weight ratio of 1.1-1.2, was studied with a Cannon-Manning viscometer and an Instron rheometer. Comparison of the flow behavior of samples with narrow and broad molecular weight distributions indicated that the onset of non-Newtonian behavior occurred at a much higher shear rate for narrow-distribution polydimethylsiloxanes than for polydisperse polydimethylsiloxanes. A plot of reduced viscosity versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma \eta _0 {M \mathord{\left/ {\vphantom {M T}} \right. \kern-\nulldelimiterspace} T} $\end{document} gave two experimental master curves, one for polymer of narrow distribution and the other for polydisperse polymer. The experimental master curve obtained from the narrow-distribution polymer was found to fit the theoretical master curve derived from Graessley's entanglement theory. The viscosity-molecular weight relationship for the higher molecular weight polydimethylsiloxanes was found to be the same for both hydroxydimethylsilyl- and trimethylsilyl-endblocked polymers. However, at low molecular weight, the viscosity-molecular weight curve deviated from linearity because of the association of polydimethylsiloxanols, which apparently is not significant at higher molecular weights. The critical molecular weight of entanglement, Mc, was found to be about 30,000.
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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1937-1953 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been considered for some time that the presence of birefringence in an oriented polymer must affect the light-scattering behavior. Previous analyses of this phenomenon are restricted to single-particle scattering. A more complete theory of the effect of birefringence on the scattering of light from correlated systems is presented. The measured scattering intensity is shown to be dependent upon the optical properties of the sample as well as the experimental technique and conditions.
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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2029-2032 
    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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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2039-2050 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Fujita equation relating molecular weight distribution to concentration of solution subjected to centrifugal forces in equilibrium proved to be an improperly posed problem in the Hadamard sense. Application of Tikhonov's regularizing functions leads to a good approximate solution of Fujita's equation. Such functions have been applied to a monomodal and a bimodal molecular weight distribution, and approximate results have been computed.
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  • 38
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2095-2103 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron-microscopic texture and physical properties of a styrene-butadiene-styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at -70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.
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  • 39
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2141-2151 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low molecular weight poly(ethylene terephthalate) samples were crystallized isothermally at 120-245°C from both the amorphous state and the melt. Isothermal annealing of these polymers at 215°C provided polymers which exhibited multiple melting peaks in thermal analysis, referred to as form I and form II, as assigned by Bell and Dumbleton. In these samples the peak temperature of the form II melting endotherm and the average crystallite size are dependent on the temperature of initial crystallization. This result requires a mechanism for retaining some structural feature during the conversion from morphological form I to form II. DSC thermograms obtained at varying heating rates on samples showing only form II endotherms support the assignment of superheating as the cause of the shift to higher peak temperatures with increasing heating rate.
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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1411-1412 
    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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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1457-1465 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect upon seeding behavior of adding well characterized fractions has been studied, so as to assess the technique as a measure of small amounts of high molecular weight. The material available to us restricted the study to fractions with comparatively low average molecular weights. Self-seeding is shown to be an extremely sensitive measure of high molecular weight tails. Knowledge of the molecular weights concerned enabled estimates to be made of the weight of molecules involved in seeding. Instability of seeds has been observed, and is explained in terms of a particular amorphous crystalline “equilibrium” within the seeds.
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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 541-554 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution parameters were determined for polymethylphenylsiloxamer fractions (5 × 104 〈 M 〈 1.5 × 106) in toluene, cyclohexane, and diisobutylamine (θ ≈ 30.4°C). The data are interpreted by the procedure suggested by Flory and Fox. Minor deviations from theory are noted. Polymers from both cis- and trans-cyclotrisiloxanes were investigated. The major portion of the work, however, was concentrated on fractions derived from the trans form. From the data obtained, a characteristic ratio of dimensions (r02/rof2)½ of 1.56 was determined. The hydrodynamic parameter Φ was determined to be (2.0 ± 0.3) × 1021. The appropriate model for the polymer is indicated to be the impermeable random coil with slight hindrance to rotation about backbone skeletal bonds.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 595-603 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of tritium-labeled sodium stearate and 35S-labeled sodium dodecylsulfate from aqueous solution on bent and on stretched polyethylene strips was directly measured. The amount of adsorption increased from 2.5 to 4.5 times on surfaces of various polyethylene samples stretched from 5.2 to 5.3 times the original length. For one sample, adsorption increased 8 and 2.5 times, respectively, on the convex and concave surfaces of a bent strip. Autoradiographs of the strips taken after adsorption revealed the appearance of both homogeneous and heterogeneous adsorption on the stretched surface of the polyethylene. The electron micrographs of the strips showed that many small fissures, about 1-5μ in length, formed on their surfaces after the strips were bent or stretched. Enhanced adsorption of the surface-active substance along these fissures was suggested. On the basis of these observations, it is proposed that in stretching or bending, fissures increase adsorption of the detergent, and the adsorption in turn promotes further development of fissures. Thus, bending and adsorption mutually promote the growth of fissures which finally result in failure of the polyethylene.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 655-656 
    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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  • 45
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 689-703 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reduced specific viscosity of poly(methacrylic acid) has been studied in ethanol-0.002N HCI solvent mixtures as a function of polymer concentration, alcohol concentration, and temperature. In addition, experiments were performed at different HCI concentrations and with KCI instead of HCI. Both intrinsic viscosity and Huggins coefficient were shown to undergo unusually strong variations. Two minima and two maxima could be demonstrated in intrinsic viscosity. The Huggins coefficient seems to show corresponding variations. The first minimum in intrinsic viscosity indicates that the coil volume has collapsed almost to an Einstein sphere. In this region the Huggins coefficient is extremely large (of order 102) and is controlled by coil association. It was shown that several forms of intramolecular interaction must be assumed to be competing to account for this behavior. The presence of HCI, particularly in the preponderantly aqueous phase, is required to suppress the polyelectrolyte effect. It is found, however, that the behavior of the solutions at relatively high ethanol concentrations is more sensitive to HCI content than is that of highly aqueous solutions. KCI can be used to replace HCI over most of the range. Increase in temperature shifts the turning points of the curves to lower alcohol concentrations. Some evidence has been found that the association constant giving rise to dimers increase with rate of shear. The importance of poly(methacrylic acid) as a chemically simple model substance for various biopolymer effects is stressed.
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 747-752 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Growth rates of G of low-melting spherulites in fractions of trans-1,4-polyisoprene have been measured. The data were analyzed by use of an equation, ln G = ln G0 - ΔF*/RTc, valid at temperatures close to the equilibrium melting point. Plots of ln G against a function of the critical free energy of nucleation ΔF* result in a family of straight lines having a common intercept, ln G0, which is independent of molecular weight. The slope of these lines is a measure of the interfacial free energy of the crystallites and increases with the molecular weight, reflecting increasing irregularity in the structure of the semicrystalline mass. Comparison of growth rates of low-melting and high-melting trans-1,4-polyisoprene indicates that G0 does not, to a first approximation, depend on the nature of the crystals growing from the melt. The temperature at which spherulites of the two crystalline forms grow at equal rates has been calculated.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 489-497 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A quantitative theoretical calculation is made of the effect of birefringence of the surrounding medium on the light-scattering pattern from a two-dimensional anisotropic spherulite. The calculated modification of the light-scattering pattern is in accord with the prediction previously made on the basis of qualitative considerations and model experiments.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 571-581 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansion of a butadiene-styrene copolymer filled with carbon blacks differing tenfold in mean particle size (HAF and MT) was investigated. The glass transition was unaffected by MT and was raised only 0.2°C for every 10 parts per hundred by weight of polymer of HAF black added. The coefficient of expansion of the polymer component of the composite in the rubbery region was substantially unaffected by either carbon black, but decreased markedly with increasing black loading in the glassy state. These results suggest that free volume is not altered appreciably by the presence of the filler in the rubbery state, but expands with decreasing temperature below Tg. The latter effect is explained by dilatation due to stresses set up around filler particles, arising from differences in the expansion coefficients of filler and polymer, which are not relieved in the glassy state. The near invariability of Tg and of the rubbery fected by adsorption of polymer segments on the carbon black surface. A conservative rough estimate indicates that restriction of segmental motion is confined to a 30 Å layer around the particles in which Tg is elevated by only 10°C.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 637-642 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 653-654 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 705-712 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic viscosity of poly(methacrylic acid) has been studied in mixtures of 0.002N HCI and a series of aliphatic alcohols. The behavior found previously with ethanol is shown to apply in the case of admixture with methanol, n-propanol, and 1,2-ethanediol. The intrinsic viscosity first drops to a minimum and then increases sharply to a maximum. With ethanol and n-propanol the maximum is followed by another minimum and maximum. With methanol and 1,2-ethanediol this effect is absent or much smaller. Methanol and 1,2-ethanediol are equivalent, molecule for molecule, in their influence on the intrinsic viscosity. With ethanol and n-propanol there are in addition one and two shoulders, respectively, in the passage from the first minimum to the first maximum. Good correlation of the data is obtained if alcohol concentration is plotted as the mole fraction of carbon atoms per OH group (in the alcohol). The first maximum in particular was shown to correspond to the point where the number of water molecules per alcohol in the solvent mixture equals the number of C atoms per hydroxyl in the alcohol. The shoulders and first minima were found to correspond to other simple ratios. This behavior reflects changes in alcohol-water structure. The maximum in the case of ethanol was found to be the most pronounced and ethanol seems to possess optimal properties from this point of view.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 739-745 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dc conductivity of poly(sebacyl piperazine), a polyamide prepared from the secondary diamine piperazine, in which no N—H groups are present and no hydrogen bonding can occur, has been examined and compared with that of a normal 610 polyamide. The results obtained point clearly to the conduction in the 610 polyamide being electronic below about 100°C but probably involving protons as well as electrons above this temperature. This is largely consistent with the findings of earlier work and clarifies the nature of conduction below about 80°C as being almost certainly electronic where previously it was in doubt. A definite and sometimes marked hysteresis in the conductivity was observed with regard to raising and lowering the temperature of the polyamides. This is explained in terms of the space-charge polarization developed in the materials at higher temperatures and which becomes clearly evident in their dielectric behavior. This shows the importance of discharging specimens at a sufficiently high temperature before making conductivity measurements. The polarization is a bulk and not an electrode effect, and it will probably depend to a marked extent on the morphology of the polyamides.
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  • 53
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the NMR second moment of a uniaxially oriented sample of polyethylene single crystals in the range of temperatures from -196°C to 130°C and its dependence on the alignment angle γ between the orientation axis (preferential direction of the molecular chains) and the NMR magnetic field are presented. The experimental results are discussed mainly with respect to the high temperature relaxation, called the α process, in polyethylene. They are compared to theoretical predictions made for a number of mechanisms of molecular motion in Part I of this work. Only one of the mechanisms considered is found to be in quantitative agreement with experiment, the mechanism here referred to as flip-flop motion. This consists of thermally activated rotational jumps of the crystalline chain segment between folds around its axis between two equilibrium sites in the lattice. Each rotational jump through 180° is accompanied by a shift of the molecule along its axis by one CH2 group. The discussion of the low-temperature relaxation of polyethylene, the γ process, is based partly on the above measurements and partly on measurements of second moments for unoriented polyethylene samples varying widely in morphology and noncrystalline content. The decrease of the second moment observed with these samples between -196°C and 20°C is taken as a measure of the intensity of the γ process. A linear correlation is found between the decrease in the second moment, designated ΔS, and the noncrystalline content, 1 - αm; this can be represented by ΔS = 1.4 + 22.1(1 - αm). It is shown that neither the crankshaft mechanism not the kink mechanism is able to account quantitatively for this result. The model of a chain end moving in a vacancy fails to adequately describe the angle dependence of ΔS in oriented polyethylene single crystals. The “sandwich model” of a polyethylene single crystal, in which the crystalline core is covered by noncrystalline surface layers, is in better agreement with observations.
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  • 54
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 813-813 
    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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  • 55
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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 shown that the Hirai-Eyring model for the liquid state is capable of accurately describing the p, V, T behavior of liquid polymers in the temperature range over which measurements are now made, and below. Once the parameter choices necessary to accomplish the fit are made for a particular polymer, the excess thermodynamic functions (differences in properties, liquid less solid) are determined by the same parameters. Above the glass transition temperature Tg the volume, excess enthalpy, and square of the excess entropy are predicted by the model to be essentially linear with temperature, in agreement with experiment. Below Tg, these functions do not remain linear (as is usually assumed in extrapolating the equilibrium behavior to low temperatures), but instead they rapidly approach zero in a continuous way as the temperature is lowered. These remarks apply to glass-forming materials composed of small molecules, as well as to polymers. The “paradox” raised by Kauzmann is thus resolved, and the Gibbs-DiMarzio second-order transition appears to be unnecessary.
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 979-990 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have measured the relaxation modulus in the temperature range 150-220°C of two samples of poly(vinyl chloride) resin with different molecular weights. The data were treated by the principle of reduced variables to yield composite curves. The shift factors (aT) when plotted against reciprocal temperature gave good straight lines from which apparent activation energies were obtained. An apparent activation energy of 50 kcal/mole was obtained for both samples. A relaxation spectrum for each resin was calculated from the relaxation modulus data. These spectra showed a marked molecular weight dependence. The spectra were in the range characteristic of the terminal zone of the entanglement plateau. Zero-shear-rate viscosities were obtained from the integration of relaxation modulus plots. From extrapolation of capillary viscosity data it is shown that the viscosity of the higher molecular weight resin used in this study does not approach its zero-shear value until shear rates less than 10-3 sec-1 are reached. The effect of supermolecular flow units is briefly discussed.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1015-1026 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of small-angle scattering produced by polarized light from stretched and annealed polymer systems containing spherulites yields information on the supermolecular transitions that occur during such treatment. A series of semicrystalline polymer systems (films, fibers) show that stretching leads to deformation of spherulites and subsequent transformation to an orientational supermolecular order. The size of the single element C2 of the supermolecular order in the direction of stretching, determined from the distance between the layer lines of the scattering pattern, is related to the diameter D0 of the initial spherulites by the relation C2 = KD0λs, where λ, is the draw ratio of the macrosystem and K is a parameter determining the deformability of the spherulites. For polyethylene at room temperature K is unity and for polychloroprene it is 1.2. Changes of C2 after annealing and restretching of the systems also obey this ratio.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1073-1087 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A convenient pressure apparatus was designed for crystallization of high polymers under hydrostatic pressure up to 5000 atm. Melt crystallization as well as heat treatment under various temperatures and pressures was carried out on several polymers, and the effects of pressure on the molecular and crystal structures of the samples are discussed. Heat treatment of syndiotactic polypropylene under high pressure yields a new crystal modification rather than the previously known helix and planar zigzag modifications. Of the three modifications of poly(vinylidene fluoride), modification III was found as a high-pressure phase for specimens in the unoriented state, while modification I was obtained as the most stable one on heat treatment of oriented specimens under high pressure. Heat treatment under high pressure converts ordinary isotactic poly-4-methylpentene-1 with a lower density than the noncrystalline value, to a new crystal modification with higher density. As is reasonable, the dense modification is stable in a high-pressure range. For these three cases, the orientation of specimens was found to remain unchanged during the transitions, which must therefore occur in the solid state.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1137-1157 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering of light by a two-dimensional spherulite of radius R is calculated when there is disorder of optic axis orientation with respect to the radius. Special cases are considered when (1) the disorder occurs in the radial direction only, (2) the disorder occurs in the angular direction only, (3) there is combined radial and angular disorder, and (4) the optic axis makes a constant angle with the radius but there is disorder in the twist angle about the axis. In all of these calculations, a correlation function for disorder is defined and the scattering pattern depends on the ratio of the associated correlation distance to the size of the spherulite. With decreasing correlation distance, the azimuthal dependence of the scattering becomes less and there is a change in the variation of scattered intensity with scattering angles in a manner dependent upon the type of disorder.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1187-1194 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nonrandom orientational distribution of structural units, such as crystallites and chain segments, prevailing in an anisotropic bulk polymer sample can be represented fully by an orientation distribution function. Measurements of fluorescence polarization and wide-line NMR are, in principle, capable of yielding information on the moments of the distribution function up to the fourth order. This work presents the method of analysis required to determine these moments. For this purpose, the distribution function is expanded in a series of generalized spherical harmonies. The method is an extension of a similar technique previously proposed for analysis of x-ray diffraction data for determination of a complete crystallite orientation distribution function.
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1195-1209 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strain-optical coefficient and relaxation modulus were simultaneously measured for high-density polyethylene at various temperatures ranging from 12 to 100°C. Not only horizontal but also vertical shifts were necessary to obtain smooth master curves by the application of time-temperature superposition. However, the relaxation modulus decreases with rising temperature while the strain-optical coefficient increases. This behavior indicates that the variation of the relaxation modulus and the strain-optical coefficient with time can not be explained by a decrease in crystallinity with rising temperature since a decrease in crystallinity usually causes a decrease in the strain-optical coefficient with time can not be explained by a decrease in crystallinity with rising temperature since a decrease in crystallinity usually causes a decrease in the strain-optical coefficient. It was emphasized that another explanation should be sought for the vertical shift in the time-temperature superposition of the time-dependence curves of the relaxation modulus and the strain-optical coefficient at various temperatures. The master curve of the strain-optical coefficient at various temperatures. The master curve of the strain-optical coefficient or the optical distribution function of relaxation times determined from it serve to distinguish the type and thermal history of the polyethylene.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1291-1302 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes produced in γ-irradiated polyethylene by subsequent ultraviolet irradiation have been investigated by ESR measurements, ultraviolet spectroscopy, and viscometric determination of average molecular weight. The photoinduced changes depend on the wavelength of irradiation. Upon irradiation at wave length greater than 3900 Å, main-chain scission occurs by reaction of trapped allylic radicals: A reduction in molecular weight sndicated by this reaction was verified by fractionation experiments and molecular weight determinations.
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  • 63
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical representation of the transformation of an orientation function between two sets of Cartesian coordinates is discussed in terms of a series expansion of the distribution function in generalized spherical harmonics. A general procedure for calculating the mechanical anisotropy of a single-phase system (a polycrystalline material) from the orientation of its structural units and the intrinsic mechanical anisotropy of the structural unit is discussed in relation to the transformation of the orientation distribution function, i.e., mutual conversion of the coefficients in the expansion of the distribution function between the two sets of Cartesian coordinates. The procedure is extended to a two-phase systems (semicrystalline polymers) containing structural units composed of crystalline and noncrystalline materials in three different geometrical arrangements.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1387-1393 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene adipate), poly(ethylene suberate), and poly(ethylene sebacate) were synthesized by a modified ester interchange procedure. Polydispersity was reduced and low molecular weight material removed by fractional crystallization. Samples of 50-60% crystallinity were prepared by bulk crystallization and annealing. Melting points and amorphous densities were obtained by dilatometry. Melting points were 7-12°C higher than previously reported. Heats of fusion were measured by differential scanning calorimetry and extrapolated to 100% crystallinity by using measured amorphous densities and recently redetermined crystalline densities. Entropies of fusion were calculated and separated for the first time into volume expansion and conformational contributions.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1057-1072 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties of poly(vinylidene fluoride) have been studied in the frequency range 10 Hz to 100 kHz at temperatures between -196 and 150°C. Three dielectric relaxations were observed: the α relaxation occurred near 130°C, the β near 0°C, and the γ near -30°C at 100 kHz. In the α relaxation the magnitude of loss peak and the relaxation times increased not only with increasing lamellar thickness, but also with decrease of crystal defects in the crystalline regions. In the light of the above results, the α relaxation was attributed to the molecular motion in the crystalline regions which was related to the lamellar thickness and crystal defects in the crystalline phase. In the β relaxation, the magnitude of the loss peak increased with the amount of amorphous material. The relaxation times were independent of the crystal structure and the degree of crystallinity, but increased slightly with orientation of the molecular chains by drawing. The β relaxation was ascribed to the micro-Brownian motions of main chains in the amorphous regions. The Arrhenius plots were of the so-called WLF type, and the “freezing point” of the molecular motion was about -80°C. The Cole-Cole distribution parameter of the relaxation time α increased almost linearly with decreasing temperature in the temperature range of the experiment. The γ relaxation was attributed to local molecular motions in the amorphous regions.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1127-1136 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory for scattering of light from films in which the orientation correlation between two scattering elements depends upon the angle β between the optic axes and the vector connecting the two elements is extended. A delta-function type dependence is assumed in which the correlation is strongest when β equals some preferred value β0. Calculated results of scattered intensities are shown to be similar to experimental observations.
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  • 67
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    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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  • 68
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    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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  • 69
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    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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  • 70
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    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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  • 71
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    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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  • 72
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    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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  • 73
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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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  • 74
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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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  • 75
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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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  • 76
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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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  • 77
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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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  • 78
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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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  • 79
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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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  • 80
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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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  • 81
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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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  • 82
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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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  • 83
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    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
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  • 84
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 8 Ill.
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  • 85
    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.
    Additional Material: 16 Ill.
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  • 86
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    New York : Wiley-Blackwell
    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.
    Additional Material: 6 Ill.
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  • 87
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    New York : Wiley-Blackwell
    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.
    Additional Material: 10 Ill.
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  • 88
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    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 14 Ill.
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  • 89
    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.
    Additional Material: 10 Ill.
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  • 90
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
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  • 91
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    New York : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
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  • 92
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    New York : Wiley-Blackwell
    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.
    Additional Material: 20 Ill.
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  • 93
    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.
    Additional Material: 7 Ill.
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  • 94
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    New York : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
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  • 95
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    New York : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
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  • 96
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    New York : Wiley-Blackwell
    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.
    Additional Material: 9 Ill.
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  • 97
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    New York : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
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  • 98
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    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
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  • 99
    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.
    Additional Material: 10 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
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