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  • 1995-1999
  • 1965-1969  (1,973)
  • 1967  (1,973)
  • Polymer and Materials Science  (1,642)
  • Industrial Chemistry  (331)
  • Nuclear reactions
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Years
  • 1995-1999
  • 1965-1969  (1,973)
Year
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 263-270 
    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 iodine by rayon tire yarn samples from aqueous solutions in which the concentration of iodide and triiodide ions is suppressed was studied. Fowler and Guggenheim's model of adsorption on regular localized monolayers appeared to be applicable to the adsorption phenomena considered. It is concluded that adsorption takes place on patches of sites in the cellulose-water gel.
    Additional Material: 3 Ill.
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  • 102
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 271-276 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NMR linewidth studies of molecular motion in several polyacrylonitrile samples have been carried out. The motional transition temperature is found in the 105-124°C. range and depends upon polymerization conditions. In addition, the thermal activation energy for the motional process underlying this transition was evaluated at 16.4 kcal./mole. Finally, measurement of the transition temperature for one of the specimens in three different physical states (bulk, spun only, and spun and drawn with a ratio of 3:1), revealed that no change in the transition temperature was effected by either spinning or drawing.
    Additional Material: 3 Ill.
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  • 103
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 361-375 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polysaccharide of salep orchid tuber was shown to be a glucomannan with a glucose/mannose ratio of 2.6 and an acetyl content of 2.1%. After extraction from the powdered root with water, the triacetate derivative was prepared and its configurational and hydrodynamic properties examined. The polymer yielded a series of fractions from 615 to 4170 in weight-average degree of polymerization. Light-scattering, viscosity, and osmometry experiments were conducted. Intrinsic viscosity results were interpreted according to the hydrodynamic theory of Eizner and Ptitsyn resulting in a value of ζ/η0 = 20 ± 6 A. for the ratio of monomeric friction coefficient to solvent viscosity and a corresponding value of a = 55 ± 4 A. for the persistence length, closely similar to those reported for other β-1,4-linked polysaccharides. The theoretical Flory coefficient increased with increasing molecular weight but was less than the limiting value of Φ0 = 2.86 × 1023 mole-1. The dependence of the light-scattering radius of gyration of the glucomannan polymer on the contour length showed that the configuration of the heteropolymer was similar to that of other β-1,4-linked polysaccharides which have only glucose or mannose in the main chain. Calculated radii of gyration based on the Porod-Kratky persistence length were found to be smaller than radii found by light scattering on the fractions.
    Additional Material: 7 Ill.
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  • 104
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 394-396 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 105
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 377-390 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentrations and the growth rates of high- and low-melting type spherulites of trans-1,4-polyisoprene were measured in the temperature range 39-49°C. It was shown that above about 40°C., the crystallization rate of trans-1,4-polyisoprene is determined primarily by the radial growth rate of high-melting form (HMF) spherulites, whereas the predominance of the low-melting form (LMF) crystals below 40°C. can be attributed to the high rate of formation of LMF primary nuclei at lower crystallization temperatures. Temperature-independent rate parameters were calculated from optical and dilatometric measurements and were found to be in good agreement. Both the change in nucleation habit and spherulite growth rate with temperature can be explained on the basis of a lower end surface free energy of LMF crystals of trans-1,4-polyisoprene compared to that of the HMF crystals.
    Additional Material: 8 Ill.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 397-397 
    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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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 417-424 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The length of the span of the terephthaloyl residue in poly(ethylene terephthalate) guarantees independence of the conformations of successive repeating units of the chain. Interactions within units of the chain are amenable to interpretation by comparisons with related polymers; cis and trans conformations of the terephthaloyl residue are given equal weighting. The mean-square dimension ratio (〈r2〉0/M)∞ estimated on this basis is in substantial accord with the value deduced from experiments.
    Additional Material: 3 Ill.
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  • 108
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 425-429 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The error analysis for the transient vibrating reed test is developed based on a linearized approximation. Tables are given for the efficient utilization of the equations in evaluating the accuracy range of test data.
    Additional Material: 4 Tab.
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  • 109
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 431-454 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationships between molecular weight distribution and structure in polymerizations with long-chain branching were reviewed and extended. Results were applied to an experimental examination of intrinsic viscosity in polydisperse, trifunctionally branched systems. Several samples of poly(vinyl acetate) were prepared by bulk polymerization under conditions of very low radical concentration. The relative rate constants for monomer transfer, polymer transfer, and terminal double-bond polymerization were established from the variation of Mn and Mw with the extent of conversion. Average branching densities were then calculated for each sample and ranged as high as 1.5 branch points/molecule. Intrinsic viscosities [η]B were measured in three systems: a theta-solvent, a good solvent, and one that was intermediate in solvent interaction. These results were compared with calculated viscosities, [η]L, which would have been observed if all the molecules had been linear. The values of [η]B/[η]L were substantially the same in all three solvents. The variation of this ratio with branching density was compared with the theory of Zimm and Kilb as adapted to polydisperse systems. Discrepancies were noted, and the adequacy of present model distribution functions for branched polymers was questioned.
    Additional Material: 6 Ill.
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  • 110
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 455-460 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the size and shape of the torsional potential upon the theoretical temperature coefficient (T∂ ln 〈r02〉/∂T) of a polymeric chain was studied. The uncorrelated end-to-end distance equations for isotactic, syndiotactic, and completely atactic chains were differentiated with respect to temperature and the integrals in the resulting equations were evaluated by the method of Gaussian quadrature. The calculated coefficients were found to be nonlinear functions of the energy ratio Umax/KT, where Umax is the maximum potential barrier and possess real roots which critically depend upon the size and shape of the potential. Qualitative anomalies between experiment and theory disappeared when the entire torsional potential was used in the conformational theory. It appears that quantitative agreement between theory and experiment can be established for polymeric materials if the entire potential is used, rotations within bulky side groups are included, and the potential is determined by the method of minimum conformational energy.
    Additional Material: 3 Ill.
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  • 111
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 471-478 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aqueous solutions of phosphotungstic acid were used to stain melt-crystallized polypropylene which had been oxidized to the leveled-off stage by boiling in 70% HNO3. Electron microscopy of thin sections of the polymer revealed unstained crystalline lamellae bordered by stained interlamellar layers. The lamella height, which is equivalent to the fold period of the molecules, increased as the crystallization temperature increased. In polypropylene which had crystallized in ice water, and at 125, 145, or 161°C., the heights of the visually delineated lamellae were 80, 105, 158, and 210 A., respectively. Those heights were, in turn, approximately the same as the length of the perpendicularly aligned molecules in the lamellae, which survived the acid etch. The stained interlamellar layers, regardless of the crystallization temperature, were about half the height of the lamellae.
    Additional Material: 4 Ill.
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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 663-670 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.
    Additional Material: 3 Ill.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 671-684 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of water sorption at 25°C. has been determined for a number of polyacetal films differing in structure, density, and orientation induced by extrusion. The equilibrium water uptake was found to be a linear function of density only; no other effect of structure or orientation was detectable. The extrapolated density for zero sorption was 1.51 g./cc., not far from the theoretical crystalline density. The diffusivity of water in unoriented films rose with decreasing density; for linear copolymer, the trend was parallel to that of the area under the dynamic mechanical loss peak associated with long-range chain motions in the disordered regions (β-transition). Less pronounced effects of molecular weight and long chain branching on diffusivity were also noted. Films crystallized while an extruded melt was still oriented showed considerable increases in water diffusivity, but no significant changes in the apparent activation energies of permeation (about 6.6 kcal./mole) or diffusion (about 11.5 kcal./mole). On annealing these films, the diffusivity remained almost constant while the sorption coefficient and retraction on remelting decreased.
    Additional Material: 5 Ill.
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  • 114
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 685-696 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cavity model used in the theory of dielectrics was applied to hydrodynamics to calculate the force exerted by a system of soft dumbbells on a reference dumbbell in a hydrodynamic field. The influence of this force on the viscosity and flow birefringence and its dependence on both the concentration and velocity gradient were calculated. The system of equations has a real solution only for values of β = M[η]η0γ/RT which are smaller than a critical value rapidly decreasing with increasing concentration. At zero concentration the results obtained agree with the theory of a single isolated dumbbell model. The calculated Huggins constant is k′ = 0.4. The extinction angle is connected with the relative viscosity very nearly as derived from experiments. However, the theory fails at higher concentrations and gradients yielding an increase in viscosity with the gradient and infinite zero-shear viscosity for the concentration c = 2.5/[η].
    Additional Material: 5 Ill.
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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 697-704 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the spin-lattice relaxation times (T1) of solvent protons have been performed on systems containing mixed solvents with and without polymer. It has been found that the motion of solvent is selectively affected by polymers present in the system. Polyisobutylene (10%) in mixed solvents of carbon tetrachloride (or cyclohexane) and dichloromethane at various proportions produces little effect on T1 values of dichloromethane, but it affects significantly the T1 values of cyclohexane; whereas poly(methyl methacrylate) (10%) in carbon tetrachloride and dichloromethane (or acetone) selectively associates with dichloromethane (or acetone), resulting in an approximate 50% reduction of the T1 values for dichloromethane (or acetone). In systems of poly(methyl methacrylate) and three mixed solvents of carbon tetrachloride, dichloromethane, and cyclohexane, the polymer (10%) has a negligible effect on the T1 values of cyclohexane, but brings about a 50% reduction of the T1 values of dichloromethane. These phenomena are discussed in terms of local selective interactions between the solvent molecules and the polymeric chain segments.
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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 711-742 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general method is presented for taking into account changes in volume in several types of calculations concerned with spherulite deformation in semicrystalline polymers. The method is applicable at large strains for which the low-strain limiting form of the equation defining Poisson's ratio is no longer valid. Applications are made to calculations of the three crystal orientation functions for models of spherulite deformation based on those proposed by Wilchinsky, Stein et al., and Oda et al. The effects of changes in volume are considered in detail and are compared with previous results in which the volume change was neglected. Calculations of spherulite birefringence are considered in a similar manner, as are the equations for determining spherulite deformation by means of low-angle light-scattering measurements. Results indicate that in several cases details of deformation mechanisms previously proposed should be revised in light of the effect of the change in volume on the calculated orientation functions. The equations in each case are presented in terms of a parameter β, the square root of the third strain invariant of the deformation tensor. Results are presented in numerical form for many of the basic parameters. Equations for all such results are expressed in explicit form and, in most cases, are displayed graphically together with available experimental data.
    Additional Material: 9 Ill.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1055-1059 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of evaluating osmotic coefficients of polyelectrolyte solutions is suggested for systems in which a two-phase equilibrium is maintained between the polymer solution and a polymer precipitate so that the “polymer” terms Cpdμp in the Gibbs-Duhem relationship may be neglected. The method is applied to a polybase system, and the osmotic coefficients calculated from the experimental data are discussed in terms of the theory of Alexandrowicz. The results are found to be in line with the above theory but the characteristic parameter φp, the fraction of free counterions, is about twice as large as values previously observed in polyacids.
    Additional Material: 2 Ill.
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  • 118
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1087-1101 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of long-chain branching on the size of low-density polyethylene molecules in solution is demonstrated through solution viscosity and molecular weight measurements on fractionated samples. These well-characterized fractions are analyzed by gel permeation chromatography (GPC), and it is shown that the separation of the polymer molecules by this technique is sensitive to the presence of long-chain branching. By using fractions of branched polyethylene possessing differing degrees of branching, one observes that a single curve is adequate in relating elution volume to molecular weight. This calibration curve is applied in the GPC analysis of a variety of commercial low-density polyethylene resins and it is shown, by comparison with independent osmometric and gradient elution chromatographic data, that realistic values for molecular weight and molecular weight distribution are obtained. The replacement of molecular weight M by the parameter [η]M as a function of elution volume, leads to a single relationship for both linear and branched polyethylenes. This indicates that GPC separation takes place according to the hydrodynamic volumes of the polymer molecules. The comparison of data for polyethylene and polystyrene fractions suggests that this volume dependence of the separation will be observed for other polymer-solvent systems.
    Additional Material: 8 Ill.
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  • 119
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1103-1118 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on wettability of elastomers should be considered basic to the understanding of all phases of elastomer adhesion. However, no such data in the form of critical surface tensions were available for elastomers other than polydimethylsiloxane. For this study, 18 elastomers were selected to determine the effects of functional groups, of geometrical and structural isomerisms, of copolymerization, and of the induced orientation upon wettability. Most results support the constitutive law of wettability established by Shafrin and Zisman. The effect of structural isomerisms in the form of a vinyl side group and cyclization is discussed. An equation for the calculation of critical surface tension of a copolymer or of a mixture of isomers is proposed as follows: \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _c {\rm (copolymer or mixture of isomers)} \simeq \sum\limits_1^\infty {N_i \gamma _{c_i } } $\end{document} where Ni is the mole-fraction of the individual monomer in the copolymer and \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _{c_i } $\end{document} is the critical surface tension of each homopolymer. Most elastomer adhesion studies conducted in the past were concerned with the diffusion theory of adhesion. This study further supports the conclusion on the role of diffusion and adsorption in adhesion advanced in Part I, especially with respect to the physical state of polymer at the time of application. The wettability data in this study could shed some light upon major basic mechanisms involved in elastomer reinforcement.
    Additional Material: 7 Ill.
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  • 120
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1119-1144 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data obtained from stress-strain curves of five different textile fibers, at a series of different, constant strain rates covering a range of 61/2 decades have been used to study two methods of nonlinear viscoelastic analysis proposed elsewhere. According to the first of these, time and strain effects are factorizable so that stress σ, strain ε and time t are related by the equation σf1(ε)/ε = f(t),. This is shown to be unsatisfactory with the present materials, but an empirical modification to σf1(ε)/ε = f2(ε) + f(t) is satisfactory. According to the second, general nonlinear viscoelastic behavior can be described by an equation which reduces to the form σ/ε = F1(t) + εF2(t) + ε2F3(t) + when applied to extension at a constant strain rate. This series is shown to be strongly divergent except at fairly small stains. In fact, if it is truncated after about three terms, which are as many as can be estimated with any significance in the present experiments, it is applicable only to strains of about 3-4% and less. Numerical techniques which enable standard statistical procedures to be used have been devised to perform the above analyses and are described in detail.
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  • 121
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of the equilibrium distribution of a mixture of different size species of a polymer between two liquid phases is reviewed and used as a basis for the calculation of the dependence of fractionation efficiency on overall concentration, interaction coefficient (hence, choice of solvent and temperature), average molecular weight, and the spread of the molecular weight distribution in the polymer. The special case of a single type of polymer in a single solvent, for which the polymer-solvent interaction coefficient is independent of concentration, is dealt with quantitatively. The ultimate aim is to make it possible to determine systematically the optimum solvent (or mixture of solvents), temperature, and overall concentration for fractionation of a given type of polymer, having a given average molecular weight and molecular weight distribution, considering practical limitations, e. g., the total volume which can conveniently be handled and the time required to achieve a sufficiently close approach to equilibrium.
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  • 122
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1296-1299 
    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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  • 123
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1300-1304 
    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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  • 124
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    Journal of Applied Polymer Science 11 (1967), S. 171-177 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Arbitrary cure times and glass transition temperatures are reported for an epoxy resin cocrosslinked by various weight fractions of hexamethylenediamine (HMDA) and m-phenylenediamine (m-PLDA). The glass transition temperatures of the epoxy resin systems studied yielded an excellent fit to an empirical equation developed by Dyvik for copolymers. The cure time parameters were found to be a linear function of the weight fractions of each crosslinking agent present. The mechanical properties of the epoxy resins were measured by an in situ dynamic modulus technique which employed the use of a resin-coated metallic substrate.
    Additional Material: 4 Ill.
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  • 125
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Antiplasticization is applicable to polymers which contain rigid, polar groups and stiff chains, such as many bisphenol polycarbonates and polyesters, 2,2,4,4-tetramethyl-1,3-cyclobutanediol polycarbonates and polyesters, cellulose triacetate, and a commercial poly(sulfone ether). The stiffness, hardness, and tensile strength of these polymers are increased by antiplasticizers, and the elongation, impact strength, and heat-distortion temperature are decreased. The stiffness of antiplasticized polymers can be further increased by crystallization. A clear, hard, stiff, tough, self-extinguishing molding plastic with good electrical properties and improved resistance to stress cracking is obtained by antiplasticizing bisphenol A polycarbonate with 20% Aroclor 5460.
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  • 126
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    Journal of Applied Polymer Science 11 (1967), S. 871-900 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The cold drawing of synthetic polymers is generally carried out through necking at a short collar between the drawn part and the undrawn part of the fiber; if the drawing is carried out in certain organic liquids, the lengthening is realized through thousands of simultaneous necks which permit the fiber to be penetrated by a dye dissolved in the liquid. The stress-strain curves for the drawing in liquid show an important decrease in the force at the time the multiple necking are produced. This decrease is the result of an increase in the mobility of the macromolecular chains through the penetration of the organic liquid to the level of the shoulder of the necks. A morphological study has been carried out through the observation of cuts by optical microscopy, along with a utilization of the techniques of x-ray diffraction, IR spectroscopy, and electron microscopy. It was found that the liquid penetrates t̰he fiber to the level of the necking via a rupture of the interchain bonds which takes place during the change of structural following the drawing. The bonds are maintained ruptured as long as the liquid is not squeezed out by the aligning of the chains; they reform later to produce a new highly crystalline structure.
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  • 127
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    Journal of Applied Polymer Science 11 (1967), S. 949-952 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Several epoxy polymers were shown to be two-phase systems; roughly spherical floccules arranged in layers in an interstitial fluid resembling the starting materials. The size of the floccules was found to be dependent on the initial rate of cure of a given polymer. The density, hardness, glass transition temperature, etching rate, and dielectric strength were related to the floccule size. The surface layer in the epoxy polymers and in several thermoplastic polymers was found to be different from the bulk material. The properties of the surface layer are dependent on the surface energy of the mold material and on the atmospheric environment. A gradient in properties was found to extend from the polymer surface several hundred microns into the bulk.
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  • 128
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    Journal of Applied Polymer Science 11 (1967), S. 963-981 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Series of loading tests were carried out on epoxy resin specimens, at varying constant strain rates, under tension, compression, and flexure. The stress-strain relationship revealed a distinct yielding stage followed shortly by a post-yielding region of decreasing load. In all cases, results indicate linearity between yield stress and log strain rate, in accordance with Eyring's theory of viscous flow. For specimens unloaded close to the yield point, photoelastic observations revealed a residual pattern parallel to the theoretical principal shear stresses. These results, supported by additional data from other works, indicate a viscoplastic deviatoric stress-biased diffusional mechanism as the dominant factor in the yielding of an amorphous crosslinked epoxy system.
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  • 129
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    Journal of Applied Polymer Science 11 (1967), S. 1001-1008 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A simple, generalized equation of state has been developed that describes the pressure-volume-temperature behavior of both addition and condensation polymers. Use of the equation requires only that the polymer's glass temperature and density at 25°C. and one atmosphere be known. The equation applies to both amorphous and crystalline polymers for pressures up to 10,000 atm. It also appears to hold for copolymers. Polymer glass temperatures can also be estimated with the equation.
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  • 130
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of commercially prepared poly(methyl methacrylate) (Lucite) were irradiated with 13-M.e.v. electrons in the dose range 0-11 Mrad, and the induced changes in the index of refraction, density, and dielectric constant were observed. An attempt is made to interrelate the observed changes theoretically.
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  • 131
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    Journal of Applied Polymer Science 11 (1967), S. 1101-1116 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Radiation-induced solid-state polymerization in binary systems containing long-chain compounds has been investigated. Butyl stearate-methyl methacrylate and stearyl alcohol-methyl methacrylate systems have been studied in detail. In these systems insource polymerization does not occur but a remarkable post-polymerization takes place on warming after irradiation at low temperature. The limiting conversion characteristics of this post-polymerization depend greatly on the nature and the concentration of the long-chain compounds. The post-polymerization is observed to be more marked in the butyl stearate-methyl methacrylate system than in the stearyl alcohol-methyl methacrylate system, and it increases with increasing concentration of the long-chain component. An optimum warming rate and warming temperature exists for the maximum saturated conversion. Irradiation in air causes some decrease of conversion compared to irradiation in vacuo. The possible mechanism is that monomer diffuses into the crystals of the long-chain compound after melting at the eutectic temperature. The polymerization may be initiated by trapped radicals of the long-chain compound and carried out in the crystal of the long-chain compound with a smaller possibility of termination. In binary systems containing long-chain compounds, lowering of the melting point is slight, and the eutectic composition exists at the richer composition of monomer, so almost all the long-chain substance remains as excess crystals, which are suitable for holding trapped radicals. The crystal lattices of long-chain compounds may be softer than those of compounds of small molecular size. This fact is favorable for monomer diffusion. This explains why such a post-polymerization takes place only in systems containing long-chain molecules.
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  • 132
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    Journal of Applied Polymer Science 11 (1967), S. 1173-1177 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(vinyl isonicotinate) was prepared by esterification of poly(vinyl alcohol) with isonicotinoyl chloride in pyridine solution. Poly(vinyl nicotinate) was also prepared. Density, refractive index, and glass transition of the polymers were determined. The low temperature dynamic mechanical properties of poly(vinyl isonicotinate) are characterized by a relaxation effect which is associated with thermally excited motions of the pyridine rings (δ relaxation). The strong displacement of such a phenomenon toward higher temperatures, with respect to poly(vinyl benzoate), is interpreted as due to the elevated polarity of the pyridine ring.
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  • 133
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    Journal of Applied Polymer Science 11 (1967), S. 1139-1153 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An ESR study of the free-radical mechanisms of the post-irradiation reactions of cotton cellulose with acrylonitrile is reported. The effects of atmosphere, moisture content, and solutions of acrylonitrile on the yield and stability of free-radical sites in irradiated cellulose were determined. On interaction of γ-radiation from a 60Co source with cotton cellulose, long-lived free-radical sites were found within the molecular lattice. Short-lived free-radical sites were apparently also formed on chain cleavage, gave strong singlet spectra, and were readily accessible to interaction with water. Other free-radical sites were formed within regions of the cellulosic fiber which were inaccessible to moisture or aqueous solutions even after contact times as long as three days. It was suggested that long-lived free-radical sites in cellulose I (containing regain moisture) resulted from dehydrogenation at C5, and in cellulose II (containing regain moisture) resulted from dehydrogenation at C5 and dehydrogenation of the OH group or dehydroxylation at C6. When irradiated cellulose was contacted with a solution of acrylonitrile (15%) in 75% aqueous zinc chloride, the initial rate of decrease in spin concentration was higher than the rate of decrease as the time of contact increased. The ESR spectrum of the reacted cellulose, observed at -100°C., as compared with the spectrum for the irradiated cellulose, had decreased in signal strength with increase in time of contact and changed from a three-line spectrum to an ill-defined spectrum. The free radical being observed was probably due to unreacted sites in the cellulose. The extent of the graft copolymerization reaction was directly related to the initial spin concentration in the irradiated cellulose.
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  • 134
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    Journal of Applied Polymer Science 11 (1967), S. 1209-1215 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The electrolysis of solutions of p-methylbenzyltrimethylammonium nitrate or, better, p-xylylenebis(trimethylammonium nitrate) or p-xylylenebis(triphenylphosphonium chloride or bromide) in a polar organic solvent with an aluminum cathode and a platinum anode results in the formation of adherent coatings of poly-p-xylylene on the cathode. The mechanism of this reaction involves the electrochemical generation of p-xylylene and its subsequent polymerization on the aluminum cathode. Competing reactions are formation of p-xylene and reduction of the solvent.
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  • 135
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    Journal of Applied Polymer Science 11 (1967), S. 1661-1665 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A simple theory is developed which correlates the Izod impact strength of polymers with (G′100-G′300)2/G′100, where G′100 and G′300 are dynamic shear moduli at 100°K. and 300°K., respectively. The theory assumes the Maxwell element for the material and the fracture time smaller than the relaxation time. The theory is verified by experimental data for numerous polymers. Another approach which correlates the impact strength with the integrated loss factor from 0 to 300°K. is also proved valid.
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  • 136
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    Journal of Applied Polymer Science 11 (1967), S. 2021-2028 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The Hermans' average angle of orientation, the angle at 40% intensity, and the Hermans' orientation factor have been studied in raw and delignified jute and mesta fibers under different moisture conditions. It is observed that the average orientation of micelles in these fibers improves on moisture absorption and further improves when the moist fiber is subjected to tension, and that the action of water is more pronounced in delignified jute fibers. The derangement of a fraction of the regions, contributing to the x-ray pattern of these fibers, and the releasing of internal stresses have been cited here as possible caused of the phenomenon.
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  • 137
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    Journal of Applied Polymer Science 11 (1967), S. 2467-2471 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: α-Cellulose dissolves in a mixture of SbCl3, KOH, and AsCl3. The resulting product as identified by PMR and infrared spectroscopy is α-D-glucose. This product is unexpected, and an explanation for its formation is suggested.
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  • 138
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    Journal of Applied Polymer Science 11 (1967), S. 2507-2514 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Visible dichroism can be utilized as a measure of the degree of orientation of an amorphous region in a polymer. But the relations between dichroism and states of dyes in polymer must be elucidated before dichroism can be used more widely as a reliable means for study of amorphous orientation. To calculate the orientation factor for visible dichroism, it is necessary to decide the dichroism of an ideally oriented polymer chain. For this purpose, a single crystal of Congo Red was prepared and the dichroic spectrum of the crystal was measured. It was found that the dichroism of the Congo Red molecule itself is unity in a suitable wavelength region. As a result, a simple means for the treatment of dichroic spectra was given. The angle between the polymer chain axis and the principal axis of the absorbed dye molecule was discussed.
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  • 139
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    Journal of Applied Polymer Science 11 (1967), S. 2525-2531 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyacrylonitrile polymer powder was dissolved in 70% nitric acid and spun into isotropic filament through a glass nozzle of 0.5 mm. diameter in a coagulating bath of 30% nitric acid. Stretching was carried out in two stages: the first stretching was done in water at 20°C. followed by drying, and the second stretching was done in a boiling saturated solution of ammonium sulfate. The total stretching ratio was 23. These filaments were shrunk freely in water at 70-180°C. The change in orientation factors was traced by x-ray, infrared dichroism, visible dichroism, and sonic modulus methods. The relation between the reciprocal absolute temperature of thermal contraction and the logarithm of fiber length is a straight line which has two inflection points at 93 and 175°C. The orientation factors by x-ray and infrared dichroism remain unchanged up to 175°C. On the contrary, the orientation factors by visible dichroism and sonic modulus drop suddenly at about 90°C. This indicates the occurrence of relaxation of the amorphous chain at the glass transition temperature and shows the polymer is not perfect single-phase material. Orientation of crystalline and amorphous phases is stable from 100 to 170°C. in spite of considerable thermal contraction. The stability of orientation can be explained by the growth of a folded structure in the polymer.
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  • 140
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    Journal of Applied Polymer Science 11 (1967), S. 311-319 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A variety of polymers have been foamed with sulfur dioxide. Properties of the foams could be varied by choice of polymer to produce rigid, semirigid, flexible, rubbery, fibrous, self-extinguishing, and/or heat-resistant materials.
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  • 141
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    Journal of Applied Polymer Science 11 (1967), S. 251-287 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the part installment of the present paper, the authors formulated the dynamics of melt spinning by introducing a set of fundamental equations that consist of the equations of heat, force, and material balances. Some steady-state solutions were also given. Additional steady-state solutions corresponding to many different spinning conditions for polyester and polypropylene filament yarns consistently show good agreement with experimental results. These steady-state solutions that give filament cross-section A (x) and filament temperature t(x) as functions of position x are correlated with yarn qualities: yarn density and birefringence, crystallinity and molecular orientation, are correlated respectively with the speed of Polymer cooling at 100°C. and the maximum tensile stress (F/A)w acting on the filament. A transient solution of the fundamental equations computed on an IBM 1401 machine shows that the filament cross-section A at the take-up roll forms a large transient peak after a stepwise increase in the speed vy of cooling air. This agrees with experiments fairly well. The fundamental equations, therefore, clarify the dynamic relations between cooling air speed and yarn weight variations.
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  • 142
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    Journal of Applied Polymer Science 11 (1967), S. 383-387 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some crystalline organic compounds containing a β-naphthyl group stiffen rubbers considerably. This paper discusses the dynamic behavior of these systems when subjected to oscillatory strain of increasing amplitude. Modulus-strain amplitude plots similar to that in carbon black-natural rubber systems are obtained. The implication of these results to reinforcement theory is discussed.
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  • 143
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    Journal of Applied Polymer Science 11 (1967), S. 439-455 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reversible gelation of acrylonitrile-vinyl acetate copolymers in concentrated solutions has been studied with the use of various solvents. These concentrated solutions gel or become rigid with time, but they become fluid again when heated above a certain temperature called the gel melting point. A technique involving the use of mercury drops was developed to measure this transition. This temperature was evaluated as a function of solids level, water content in the solvent, and the amount of vinyl acetate in the copolymer, dimethylacetamide being used as the solvent. Four other solvents were used to obtain limited data. Gel melting was studied further by differential thermal analysis and shear modulus measurements. The results are discussed in terms of network formation and solubility. The x-ray diffraction results imply that the tie points of the gel are crystalline.
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  • 144
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    Journal of Applied Polymer Science 11 (1967), S. 425-437 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Methyl methacrylate was grafted onto cellulose using Caro's acid-Fe3+ system as initiator. The effect of grafting time, ferric ion concentration, and cellulose/monomer ratio, on the per cent grafting, was investigated. From studies of the reaction mechanism with model compounds it was postulated that the grafting did not occur at the 1,2-glycol units or at the hemiacetal unit in the end of the cellulose molecule. Concurrent degradation of the cellulose during the graft copolymerization was examined. A linear relationship between the per cent grafting and the number of cellulosic broken chains by hydrolysis was found, from which it would seem that the structure of the graft copolymer was of block-type. The structure of the graft copolymers was also studied by determination of the molecular weights of the grafted PMMA branches, after hydrolysis of the cellulosic backbone. In all cases, independently of reaction conditions, the molecular weights of the grafted branches were very high and their number low. The number of graft branches per cellulose chain was calculated from the per cent grafting, the molecular weights of the PMMA branches and of the cellulosic backbone. This number was compared with the number of cellulosic bonds broken during grafting.
    Notes: Le méthacrylate de méthyle a été greffé a la cellulose en utilisant l'acide de Caro en présence de sel ferrique comme initiateur. L'effet de la durée du greffage, de la concentration en ions ferriques et du rapport cellulose-monomere sur le pourcentage du greffage a été étudié. Au départ d'études du mécanisme de réaction, a des composés modèles, on a admis que les greffages ne se passent pas via les unités glycols 1,2 ou à l'unité hémiacétalique ' la fin de la molécule cellulosique. Des dégradations concommittantes de la cellulose en cours de la copolymérisation greffée a été examinée. Une relation linéaire entre le pourcentage de greffage et le nombre de chaînes cellulosiques briées par hydrolyse a été trouvée, d'où il semble que la structure du copolymère greffé était plutôt du type séquencé. La structure du copolymere greffé a aussi été étudiée par détermination des poids moléculaires des branches de polyméthacrylate de méthyle greffées apres hydrolyse de la chaîne cellulosique. Dans tous les cas, indépendamment des conditions de réaction, les poids moléculaires des ramifications greffées étaient tres élevés et leur nombre faible. Le nombre de branches greffées par chaîne cellulosique a été calculé au départ du pourcentage de greffage, des poids moléculaires des branches de polyméthacrylate et des poids moléculaires de la chaîne cellulosique. Ce nombre a été comparé au nombre de liens cellulosiques brisés en cours de greffage.
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  • 145
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    Journal of Applied Polymer Science 11 (1967), S. 553-566 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two mercaptosilane monomers were prepared and polymerized by oxidation to yield mercaptan functional silane polysulfide polymers. The mercaptosilane monomers were of the general formula, [HS(CH2)x]2SiY2, where x = 3 and Y = Et or Me. These monomers were prepared by the addition of thiolacetic to diallyldialkylsilanes. The dithioldiacetate that resulted from the addition reaction was hydrolyzed in alcoholic NaOH yielding the dimercaptan. Polymerization of the dimercaptan was accomplished with peroxides, iodine, or sulfur, yielding polymers of a molecular weight of approximately 1200. These polymers were cured to solid elastomers with mild oxidizing agents. The mercaptan monomers were also redistributed with diethylformal polysulfide polymers, which were then cured to solid elastomers with mild oxidizing agents. The redistributed silane-diethylformal polymers were used to make composite solid propellants. A 50% increase in propellant burning rate and a 16°C. lowering of the glass transition temperature were found when the redistributed polymer was used in place of diethylformal polymers as a propellant binder. Experimental procedures are given.
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  • 146
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    Journal of Applied Polymer Science 11 (1967), S. 575-585 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The change of the viscoelastic behavior of an unsaturated polyester resin during curing was followed by a vibrometric technique, while the portion converted to gel in applied films was also determined by means of extraction with a solvent. Some relationship between the viscoelastic properties and the amount gelling has been found to exist. The dependency of the curing rate of polyesters on the concentration of initiator as well as accelerator seemed not to be unity. A marked delay in cure has been observed in the region of low concentrations of initiator and accelerator.
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  • 147
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    Journal of Applied Polymer Science 11 (1967), S. 639-657 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The purpose of this paper is to show how a theoretical molecular weight distribution can be found which would result in a given gel permeation chromatogram. Also, to show how the method can be applied to blending problems where one desires a given molecular weight distribution.
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  • 148
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    Journal of Applied Polymer Science 11 (1967), S. 727-734 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A two-step procedure for the preparation of methyl cellulose nitrate is described. The heterogeneity of the methylation step is reflected in the nonuniformity of the products obtained by nitration with either 98% nitric acid or a solution of 98% nitric acid in methylene chloride. On the basis of the experimental data it is calculated that methyl cellulose having a minimum degree of substitution of 1.8 is required for the preparation of a uniformly substituted methyl cellulose nitrate.
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  • 149
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    Journal of Applied Polymer Science 11 (1967), S. 753-771 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polymerization of β-propiolactone (βPL) by sodium acetate catalyst has been investigated. The polymerization behavior with monomer purified with calcium chloride was found to be a little different from that previously reported for this monomer. That is, poly-β-propiolactone (PβPL) obtained from βPL dried with CaCl2 has a higher degree of polymerization than that obtained from conventionally treated βPL, and its infrared spectrum shows type II configuration, which differs from that reported in previous papers. Some chain transfer reaction is observed even for the polymerization of the CaCl2-dried βPL; however, this is less important in toluene. The electronegativity of the anion or cation in catalyst greatly influences the rate of polymerization.
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  • 150
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    Journal of Applied Polymer Science 11 (1967), S. 1009-1026 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper describes an investigation into the degradation of a purified epoxide based on the diglycidyl ether of bisphenol A hardened with p,p′-diaminodiphenylmethane. The method used was that of hot-wire pyrolysis followed by gas chromatography. Special attention was given to the problem of solid residues formed on the pyrolyzer tube, and evidence was found that these probably contain oligomers. Resonance-stabilized free radicals also appear to be formed, and evidence is found to support the idea of dehydration during degradation, originally put forward by Lee. An attempt, based on first principles, is made to explain the degradation of epoxides, using evidence from previous work as well as that described in this paper.
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  • 151
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    Journal of Applied Polymer Science 11 (1967), S. 1043-1053 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Time dependence in the melt indexing of polyolefins stabilized against thermally induced changes is well known, the prevalent effect being an increase in melt index toward a steady-state value. The melt index of polyethylenes compounded with carbon black has been found to decrease, in some cases radically, although oxygen uptake data show no evidence of thermal instability. The melt index-time plot can be restored to its normal shape by adding excess quantities of a standard thioether antioxidant. Data are rationalized by assuming that polyethylene adsorbs on the available pigment surface, forming a crosslink network. The thioether antioxidant, however, may adsorb preferentially, thereby restoring the normal response of the polymer to forces resulting in its capillary extrusion. The results emphasize the contribution of chain orientation effects to the time dependence of melt index.
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  • 152
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    Journal of Applied Polymer Science 11 (1967), S. 1079-1086 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is described for deriving by digital computer a temperature program which, when applied to batch polymerization, will keep the supply of new free radicals constant throughout the main part of the reaction.
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  • 153
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Reactions of various monoepoxides and diepoxides with diethylaminoethyl (DEAE) cellulose in the absence and presence of external catalysts have been studied. In the absence of additional catalysts, many epoxides which did not react with the unmodified cotton reacted with DEAE-cotton. Others, which reacted with unmodified cotton in the presence of external bases, imparted different properties when catalyzed by the builtin tertiary amino groups of DEAE-cotton. For example, epichlorohydrin reacted with DEAE-cotton to produce a fabric with excellent conditioned recovery, good wet recovery, and strong-base anion exchange properties. The same epoxide imparted only wet crease recovery to cotton when the reaction was catalyzed by external bases. Phenyl glycidyl ether and styrene oxide reacted with DEAE-cotton to produce a fabric with twentyfold improvement in resistance to flex abrasion. With 8% aqueous NaOH as an external catalyst, the DEAE-cotton displayed greater reactivity with all epoxides than did the unmodified fabric. DEAE-cotton-diepoxide reactions with added base catalyst generally resulted in a decrease in the conditioned recovery angle and an increase in the wet recovery angle. When Zn(BF4)2 was used as an additional catalyst, again the DEAE fabrics displayed the greater reactivity toward the monoepoxides; but the unmodified cotton was more reactive toward the diepoxides than was the DEAE-cotton. The Zn (BF4)2-monoepoxide-treated DEAE fabrics had higher wet recovery angles but lower dry recovery angles than the corresponding epoxide-finished control cottons. Butadiene diepoxide was the only diepoxide investigated which imparted higher dry recovery angles to the DEAE-cotton than to the unmodified cotton control in the presence of Zn(BF4)2. Tertiary amino groups in DEAE-cottons act as an internal catalyst for the opening of the oxirane rings, direct the site for reaction in the absence of additional catalysts, and react with some epoxides to form quaternary nitrogen groups.
    Additional Material: 5 Ill.
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  • 154
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    Journal of Applied Polymer Science 11 (1967), S. 687-698 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The oscillating flow behavior of a variety of high-density polyethylene and copolymer samples was studied in a constant displacement rate rheometer. At any plunger velocity, the period of the oscillations decreases linearly with melt depth, suggesting a resonance phenomenon. As plunger velocity is increased, the load waveform changes in a regular manner that indicates a progressive increases in the proportion of each cycle spent on the right-hand branch of the flow curve. Little difference was found in the shear stress at which oscillating flow began for samples differing in molecular weight, molecular weight distribution, and manufacturing process. However, the shear rate at which oscillating flow begins depends, strongly on both molecular weight and distribution. Oscillating flow is shifted to higher shear rates by broadening distribution, reducing molecular weight, increasing temperature, or decreasing the L/D ratio of the capillary.
    Additional Material: 11 Ill.
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  • 155
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    Journal of Applied Polymer Science 11 (1967), S. 859-870 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of the radiation-induced grafting of styrene to cellulose in methanol have been studied in air at dose rates of 0.007, 0.014, and 0.078 Mrad/hr. in 60Co and spent fuel element facilities. The variables affecting rate of grafting include monomer concentration, radiation dose rate, and total dose. Grafting reaches a maximum at 60-70% by volume methanol in styrene. The results have been interpreted in terms of possible grafting mechanisms, including charge-transfer intermediates; however, a complete mathematical treatment of the data is not possible at present because of the absence of appropriate swelling data for cellulose in mixtures of styrene and methanol. Poor grafting observed in solutions of up to 10% monomer is attributed to radical scavenging (predominantly from the solvent) by the monomer leading to the formation of scavenged products including homopolymer. Rate of grafting falls off for solutions above 80-90% monomer concentration and radical scavenging by monomer radicals is again postulated to account for the observed behavior.
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  • 156
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    Journal of Applied Polymer Science 11 (1967), S. 909-919 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ion-permselective membranes containing polyethylene in their base material have been examined by direct transmission electron micrography and x-ray diffraction. All of the electron micrographs showed white lines of about 100 A. thickness between somewhat thinner black lines composed of granules. These lines often occur as black-white-black triplets. We tentatively explain these structural elements by assuming that they are cross sections of the crystallite platelets, characteristic for polyethylene, reacted on both of their faces during sulfochlorination. It is known, that these platelets are about 100 A. thick, X-ray diffraction experiments also showed the characteristic lines of polyethylene crystallites, their intensity decreasing after sulfonation. The velocity of heterogeneous sulfochlorination of polyethylene sheets decreases abruptly when the film contains 6% S and 7% Cl (after hydrolysis). This m̰eans six substituted sites on a chain element across the platelet for a 100% crystalline film and accordingly less for a partially amorphous material. It is known that five CH2 groups of each chain element are exposed at the surface of the platelets, in good agreement with our findings.
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  • 157
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    Journal of Applied Polymer Science 11 (1967), S. 1539-1552 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A large-scale fractionation of poly(vinyl chloride) (3000 g.) has been carried out by a fractional precipitation method. The molecular weight distribution of some fractions has been controlled by refractionation. The fractions have been also characterized by viscometry, osmometry, light-scattering, and glass transition temperature measurements. The data available in literature concerning the molecular weight characterization of poly(vinyl chloride) fractions have been critically reviewed. It has been shown that most of the viscometric and osmometric data are in good agreement when the molecular weights are below 105. Above 105 the literature discrepancies can be attributed to aggregation.
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  • 158
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    Journal of Applied Polymer Science 11 (1967), S. 1571-1579 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of preheat treatment at temperatures below the glass transition for various periods of time on selected properties of molded polycarbonate has been studied. Changes in tensile and flexural strength as functions of time and preheat temperature (80-140°C.) were determined and these are discussed in relation to changes in the nature of the β-transition region and the influence of the glass transition region. It is suggested that the preheat treatment produces a greater degree of order within the amorphous region of the polymer, resulting in an increase in strength at temperatures up to 132°C. The strength of the polycarbonate before and after heat treatment appears to be independent of the presence of the equilibrium water content.
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  • 159
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    Journal of Applied Polymer Science 11 (1967), S. 1593-1602 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Gel-point calculations based on the theory of polyesterification proposed by Flory do not agree with the experimental values even when Bobalek's concept of gel point as the first formation of infinite molecules (microgel) is used. Resins covering the range 30-60% oil length were prepared and examined by electron microscopy for the presence of microgel particles. The extent of reaction at which microgel forms is discussed in relation to the concept of equal reactivity. The conditions necessary for the formation of microgel particles and the significance of these observations to the basic assumptions used in developing the theory of polyesterification are discussed.
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  • 160
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    Journal of Applied Polymer Science 11 (1967), S. 1641-1647 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermal degradation in oxygen of fifteen polymers containing aromatic rings in the chain has been studied by a weight loss method. The relative thermal stabilities of the different polymers have been determined and, where possible, the overall activation energy for breakdown. The results have been compared with those for samples of the same polymers degraded in vacuum. The most thermally stable of the polymers examined under oxidizing conditions was poly(2,6-dichlorophenylene oxide), with a stability comparable with that of a copolymer of tetrafluoroethylene and hexafluoropropylene.
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  • 161
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    Journal of Applied Polymer Science 11 (1967), S. 1667-1682 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Oil-bearing formations often consist of loose sandy material. In the production of oil from these formations sand tends to be carried to the well bore along with the oil. The flow of sand can be prevented by consolidating or cementing together the sand particles of the formation around the well bore. The cementing has to be accomplished in such a manner that fluid flow channels between particles remain open. This paper describes a new three-step process that was developed to consolidate oil well sand. The steps in the process involve injection of: (1) resin, (2) inert fluid, and (3) inert fluid containing a catalyst. In the first step of the process, resin in injected into the formation where it fully saturates the interstices between sand grains. Permeability is established in the second step by displacement of the excess resin from the interstices, thereby leaving a thin film of resin on the sand grains. In the third step, polymerization is activated by migration of catalyst from the inert fluid into the thin resin film on the sand. The process has the advantage that resin is placed and permeability is established before the resin is catalyzed. This avoids premature polymerization of the resin which might cause plugging of the formation or the tubing string used to inject resin. Desirable characteristics of a resin for the three-step process are: (1) viscosity of 25-200 cp. at well bore temperature; (2) stability for several days at well bore temperature; (3) high adhesion to sand in the presence of an inert flushing fluid; (4) polymerization by less than 10% catalyst; (5) the polymerized resin binds sand together with a strong bond that is not affected by well fluids. Five different resin types have been tested for use in the three-step sand consolidation process. These are: (1) epoxy-anhydride cured with a tertiary amine; (2) epoxy-epoxy diluent cured with a primary-tertiary amine mixture; (3) furan; (4) unsaturated polyester-vinylpyrrolidone; (5) unsaturated polyester-styrene. The two epoxy resins give strong, permeable consolidated sand which is resistant to well fluids such as brine and crude oil. The furan resin gives a weak consolidation. The unsaturated polyester-vinylpyrrolidone gives good strength and oil resistance but is sensitive to brine. The unsaturated polyester-styrene is difficult to apply. Many oil wells have been successfully treated in the Gulf Coast area and in California with the two epoxy resins. Almost all of these wells are producing free of sand, and, to date, more than five million barrels of oil have been produced from these wells.
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  • 162
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    Journal of Applied Polymer Science 11 (1967), S. 417-424 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Bueche's theory is modified to account for the effect of polydispersity on viscosity of polymeric fluids. Results indicate that the ratio of weight-average to number-average molecular weight, 〈Mw/Mn〉, though a common measure of polydispersity, is insufficient to account completely for the effect of polydispersity on viscosity.
    Additional Material: 4 Ill.
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  • 163
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    Journal of Applied Polymer Science 11 (1967), S. 1315-1323 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The fracture edge of a strip of regenerated cellulose film broken under tension can usually be divided into three regions: (A) the site of the initial failure, (B) the slow-tear region, and (C) the fast-tear region. Photomicrographs showing these regions are presented and discussed. Three different types of initial failure are described and some data presented relating the breaking strain to the type of initial failure.
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  • 164
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of the effect of catalyst (base) concentration and N-acylcaprolactam cocatalyst size and substitution on the fast anionic polymerization of caprolactam indicated that a steric effect due to cocatalyst size exists, and perhaps an electronic effect due to cocatalyst substitution was noted. The rate of polymerization, degree of polymerization, and yield of polymer are related to these effects. It was also noted that at high base concentrations, the rate and degree of polymerization along with the product yields all decrease. These latter observations suggest that reinterpretation of some of the reaction mechanism data may be important if polymer degradation is not an appreciable factor during the reaction.
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  • 165
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    Journal of Applied Polymer Science 11 (1967), S. 1361-1369 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Introduction of primary covalent crosslinks into linear, segmented elastomers was followed by observing their modulus-temperature behavior. The behavior of the linear segmented polymers is explained by association of glassy segments into regions which act as filler and quasi-crosslink. In several cases crosslinkage disrupts these regions and thereby lowers the “plateau” modulus.
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  • 166
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    Journal of Applied Polymer Science 11 (1967), S. 1431-1438 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Several phosphorus derivatives of methyl 2-(chloromethyl)acrylate, including three phosphonium salts and one phosphonate ester have been prepared. A brief study was made of their polymerization characteristics under free-radical conditions. Several factors were noted which prevented the synthesis of methyl 2-[(diethoxyphosphinyl)-methyl]acrylate in high yields in initial experiments. Homopolymerization of these phosphorus derivatives does not take place readily in the presence of free-radical initiators.
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  • 167
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    Journal of Applied Polymer Science 11 (1967), S. 1449-1460 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential thermal analyses of many 66 nylon samples have shown two endotherms in the melting range. This effect occurs with drawn nylon yarn, as previously observed by White, and also with annealed and precipitated nylon samples. Methods for the preparation of these samples are reported. At 242°C. the development from the melt of crystalline material which gives two melting peaks is associated with annealing rather than with the primary crystallization process. Previous observations of multiple melting peaks with other polymers are discussed.
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  • 168
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    Journal of Applied Polymer Science 11 (1967), S. 1475-1481 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic mechanical measurements were made with a torsional pendulum of a TiO2- filled epoxy polymer (crosslinked with hexamethylene diamine) over a temperature range from 20-90°C., at filler concentrations of 0-40 wt.-%. The second-order transition temperature (Tg) was raised as the filler content increased. The behavior of TiO2 filler results in a long-range immobilization of the highly crosslinked system with resultant increases in shear modulus (higher G′) as well as decreased capacity for energy dissipation (lower damping factor). The out-of-phase modulus (G″) increased with filler content as well. The magnitudes of the slope parameters Hr (representing G′ data above Tg) and Hg (representing G′ data below Tg) decreased with greater filler content. The possibility is set forth that the TiO2 filler causes a different distribution of mobility around the nitrogen junction as well as a change in the effective number of CH2 units between crosslinks.
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  • 169
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    Journal of Applied Polymer Science 11 (1967), S. 1603-1611 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Graft copolymerization of natural rubber and MMA was carried out in the presence of Bz2O2 or AIBN as thermal initiator and hydrogen peroxide or benzophenone as photosensitizer. From the overall copolymerization product, the rubber-PMMA graft copolymer fraction was isolated from unreacted rubber and free PMMA fractions and composition characterization of the separated fractions was done by determination of rubber unsaturation. The efficiency of grafting under different conditions has been calculated and compared.
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  • 170
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    Journal of Applied Polymer Science 11 (1967), S. 817-828 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The present paper describes the results of a preliminary study of certain physical and thermal properties of benzhydrylated cotton yarns. The 200-yd. lengths of 7/2 yarn consisting of purified mercerized cellulose were reacted in a special reactor to various degrees of substitution from DS 0.31 to DS 1.22 with benzhydryl bromide in a mixture of equal volumes of 2,6-lutidine and dimethylformamide. The products were examined for tensile strength at break, which decreased only slightly with substitution; ultimate elongation, which was relatively uniform at 60-70% of the control yarn; and tenacity, which decreased with substitution largely due to added weight. The energy of rupture remained relatively constant at about 50% above the control. Tensile stiffness decreased progressively with substitution to about 25% of the control. Density decreased 10-11% with substitution. Crystallinity of the cellulose largely disappeared with substitutions above DS 1, and the lattice of benzhydryl cellulose began to appear. Stiffness, elastic recovery and work recovery were measured on 5-in. specimens of the yarn in an oven while they were subjected to repeated extension to about 1-2% and relaxed as the temperature was raised twice to 200°C. and lowered. During the heating phase of the first cycle the yarn underwent considerable heat adaptation. However, during the cooling phase and during both heating and cooling phases of the second cycle, the yarns showed generally favorable behavior. Attempts are made to interpret the results in terms of molecular modifications.
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  • 171
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    Journal of Applied Polymer Science 11 (1967), S. 901-907 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Infrared spectral analysis has been applied for the study of cotton-polyacrylonitrile copolymers prepared by using the preirradiation method. The degree of grafting was determined from the absorption at 2249 cm.-1, which is characteristic of the polyacrylonitrile spectrum, with an accuracy of ± 1.5%.
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  • 172
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    Journal of Applied Polymer Science 11 (1967), S. 953-961 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: By means of x-ray diffraction, the lattice spacing of the (100) plane for molded polytetrafluoroethylene was measured at different temperatures from 25 to 190°C. In the crystalline region, the linear expansion coefficient, in the direction perpendicular to the molecular chain axis, was obtained as 1.1 × 10-4°C.-1 below 60°C., as 1.2 × 10-4°C.-1 above 90°C., and as a minimum value of some 0.2 × 10-4°C.-1 at about 80°C. As the linear expansion coefficient of the crystalline region in bulk was observed as some 0.6 × 10-4°C.-1, the expansion coefficient in the direction of molecular chain axis must be negative except in the transition region near 80°C. The variation of molecular chain axis separation with temperature showed an irregularity at about 80°C. but none near 130°C. in the crystalline region. Infrared absorbance of film samples of PTFE was measured at different temperatures of 25 to 150°C. range for 518, 627, and 639 cm.-1 bands. On absorbance-temperature curves for those b̰ands, irregularities were observed near 30, 50, 90, and 130°C. Particularly with 518 cm.-1 band, a more crystalline sample gave more distinct irregularities near 50 and 90°C. than a less crystalline sample. The change at about 90°C. in infrared spectra may correspond to that obtained by x-ray measurements near 80°C., which was thought to occur in the crystalline region. The results obtained by x-ray and infrared measurements support the previous results by thermal, rheological, and dielectric methods: there exist first-order transitions in the crystalline region at about 90°C. and second-order transitions in the amorphous region at about 130°C.
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  • 173
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    Journal of Applied Polymer Science 11 (1967), S. 991-999 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fractions of dimethylsiloxane polymer with viscosity-average molecular weights from 2.4 × 105 to 1.3 × 106 were dissolved in toluene in concentrations from 0.01 to 1.0 g./dl. These solutions were subjected to ultrasonic degradation at 20,000 cps for periods extending to as much as 960 min. in a water-cooled reaction vessel. Gel permeation chromatography shows that samples with different initial distributions approach the same distribution after 120 min. of degradation. Dilution of the polymer from 1.0 to 0.01 g./dl. more than triples the degradation per gram of polymer but requires 10 times as much energy per gram of polymer to degrade from a number-average molecular weight of 106 to 105. Increasing the power input from 36 to 72 w. almost doubles the degradation rate per gram of polymer.
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  • 174
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    Journal of Applied Polymer Science 11 (1967), S. 1903-1914 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The regulating efficiency of four aliphatic mercaptans was studied in emulsion copolymerization of butadiene with styrene, at +5°C. with the use of the redox system, diisopropylbenzene hydroperoxide-complexed ferrous iron-sodium formaldehyde sulfoxylate as an initiator and the sodium soap of disproportionated rosin as an emulsifier. The apparent transfer constants C of tertiary mercaptans decreased logarithmically with increasing length of molecule. This tendency is connected with the analogous dependency of solubilities of these compounds in water. The mercaptans did not affect the rate of polymerization. The value of C is independent of the amount of regulator used. With the value of C, the amount of regulator, and the conversion known, it is possible to predict the molecular weight of the polymers, except for the region of poor regulation, where the deteriorative influence of termination and crosslinking reactions takes place. The apparent transfer constant of tertiary dodecyl mercaptan decreased with increasing rate of polymerization. After elimination of diffuse processes, the value of the actual relative transfer constant was calculated. The tertiary dodecyl mercaptan has been selected as the most convenient molecular weight regulator for emulsion copolymerization of butadiene with styrene of all compounds studied for the system mentioned.
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  • 175
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The manner in which a series of silcarboranylene-siloxane polymers behave in air at elevated temperatures was investigated by thermogravimetric, isothermogravimetric, and differential thermal analyses techniques. Results indicate that methyl pendant groups on the polymers undergo thermal and oxidative degradations at temperatures under 600°C. Final weight losses of the polymers, however, are significantly lower than that shown by dimethylsiloxanes. The reduced volatility is attributed to the inhibition of thermooxidation by the m-carboranylene group in the polymer molecules. This protective influence decreases apparently as the distance between the carborane nucleus and the methyl groups increases.
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  • 176
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four α,ω-diisocyanates (tetramethylene, hexamethylene, decamethylene, and eicosane) and six α,ω-diacid chlorides (succinyl, adipyl, pimeloyl, sebacyl, dodecane, and docosane) were allowed to react with two types of nylon 66 yarn made from polymers of 14,800 and 21,000 number-average molecular weights. The higher molecular weight yarn had a more ordered structure initially, as indicated by density measurements. Both diisocyanates and diacid chlorides crosslinked the yarn as shown by insolubility in 90% formic acid. Isocyanates were more efficient crosslinking reagents than diacid chlorides. Diacid chlorides caused simultaneous degradation of the yarn. The overall rate of reaction of the reagents with the yarn responded to temperature, reagent concentration, and time as expected for low molecular weight materials bearing the same functional groups. Catalysts had only a small effect on the rate of reaction. The reaction occurred in the less ordered regions of the yarn, as indicated by (1) a faster rate of reaction with the less ordered yarn, (2) the accelerating effect of swelling solvents on the rate, and (3) the reduction in extent of reaction with increase in molecular size of the reagent even though the reaction was not limited by diffusion. Both diisocyanates and diacid chlorides reduced the dyeability of yarn with acid dyes. Diacid chlorides increased the dyeability of yarn with basic dyes and diisocyanates decreased this dyeability.
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  • 177
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    Journal of Applied Polymer Science 11 (1967), S. 2077-2078 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 178
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    Journal of Applied Polymer Science 11 (1967), S. 2097-2108 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We measured the rate of thermal decomposition of azobisisobutyronitrile (AIBN) from the rate of loss of 2,2-diphenylpicrylhydrazyl (DPPH) on reaction of the free radicals formed by thermal decomposition of azobisisobutyronitrile (AIBN) in organic solvents with DPPH. There has been some doubt about the quantitative relation between AIBN and DPPH required to get the rate constant of thermal decomposition of AIBN. In the past, AIBN has been used in excess, and the rate constants measured by using DPPH are smaller than they ought to be. In our experiments we used as little of AIBN relative to DPPH as possible and obtained a value of 3.8 × 10-4 min.-1 at 50°C. as the rate constant of the first-order reaction, which was shown satisfactorily by the linearity of the graph. We also obtained 32 kcal./mole as activation energy. We were also able to make clear the meaning of the result when a large quantity of AIBN was used.
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  • 179
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    Journal of Applied Polymer Science 11 (1967), S. 2593-2594 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 180
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    Journal of Applied Polymer Science 11 (1967), S. 2331-2341 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The separation of poly(acrylic acid) from its mixtures with polystyrene emulsion by gel filtration, without destroying the state of dispersion, was undertaken. It was found that the poly(acrylic acid) not absorbed on the polymer surface is almost completely seperated by gel filtration, if the ionic strength, in this emulsion is not so high. Furthermore, the gel filtration study revealed that poly(acrylic acid) molecules are not adsorbed on the polymer surface saturated with surfactant molecules, whereas poly(acrylic acid) molecules, when already adsorbed on the polymer surface, are not easily desorbed by adding another surfactant.
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  • 181
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    Journal of Applied Polymer Science 11 (1967), S. 2343-2348 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The process of solid-phase crystallization in poly(ethylene terephthalate) has been followed by means of differential enthalpic analysis. Kinetic data for the process has been obtained for isothermal annealing from 100 to 115°C., showing induction times and first-order rate dependence. For the material studied, undrawn polyester filaments, an activation energy of 44 kcal./mole was determined. The technique used provides more direct monitoring of the crystallization phenomenon than that achieved with other methods.
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  • 182
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    Journal of Applied Polymer Science 11 (1967), S. 2361-2372 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An electron-microscope technique is presented to permit detailed examination of the fine structure of the rubber particles in reinforced polystyrenes. Several rubber-modified polystyrenes, prepared by different methods, have been examined by this technique, and the resulting photomicrographs compared with those of the previously used phase contrast method. Polymers produced by the agitated-solution process are examined in more detail. It is shown that the rubber particle fine structure is basically unaltered as the amount or type of rubber is changed or if the polymer is diluted by mechanically blending with polystyrene. It is characterized by the presence of numberous polystyrene occlusions within the particle.
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  • 183
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    Journal of Applied Polymer Science 11 (1967), S. 2373-2379 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(methyl methacrylate) has been photolyzed with 2537 A. radiation in dioxane and in methylene chloride at about 25°C. in the presence and absence of air. In degassed solutions, quantum yields for random scission are only slightly affected by either intensity or polymer concentration. Oxygen is an apparent inhibitor for photodegradation. The inhibiting and sensitizing effects of a variety of added solutes, including aromatic hydrocarbons, aliphatic dienes, and ketones were investigated; the behavior is similar whether or not oxygen is present. The results are best explained on the basis of an electronic energy transfer mechanism involving the lowest excited triplet levels of the polymer and the added solutes.
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  • 184
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    Journal of Applied Polymer Science 11 (1967), S. 2397-2398 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 185
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    Journal of Applied Polymer Science 11 (1967), S. 2485-2497 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The physical properties of nylon 66 yarn treated with α,ω-diisocyanates (tetramethylene, hexamethylene, decamethylene, and eicosane) and diacid chlorides (succinyl, adipyl, pimeloyl, sebacyl, dodecane, and docosane) were compared to the properties of a control exposed to the same reaction conditions but without the reagent being present. Two types of yarn were used: (1) a highly ordered yarn, as judged by density and x-ray, from polymer of number-average molecular weight 21,000; and (2) a less-ordered yarn from polymer of molecular weight 14,800. Treatment was carried out with yarn in both constant-length and relaxed conditions. The properties were changed most by constant-length treatment and by the use of less-ordered yarn. Treatment with diisocyanates resulted in an increase in the tenacity and modulus simultaneously. The strength properties often went through a maximum as a function of the degree of reaction. Treatment with diacid chlorides degraded the physical properties as a result of polymer chain scission and weakening of the interchain forces. Treatment with either type of reagent lowered the zero strength temperature, but had little effect on the moisture regain or ability of the yarn to dissipate static electricity.
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  • 186
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    Journal of Applied Polymer Science 11 (1967), S. 2515-2523 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The orientation factor by infrared dichroism of polypropylene film was compared with the other orientation factors. After the correction of imperfect polarization and the suitable choice of the base line, it was found that infrared dichroism is a reliable indicator of the orientation factor. Orientation factors obtained from the 998 and 842 cm.-1 bands agreed with the x-ray orientation factor, and that from the 975 cm.-1 band agreed with the optical orientation factor.
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  • 187
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    Journal of Applied Polymer Science 11 (1967), S. 289-296 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mercerization behavior at 20°C. of Valonia macrophysa cellulose of Japanese origin was investigated by x-ray, moisture regain, and infrared spectrographic methods. The NaOH concentration range necessary for mercerization was 16-20%, which is higher than those required for wood pulp (8-11%), ramie or cotton (11-14%), and even the animal cellulose, Tunicin (14-16%). Treatment with the alkaline solution of the ordinary concentration (17.5%) for 4 days could not mercerize it, and even mercerization with a 19% solution brought about the presence of the reflection from (101)II along with those from (101)I and (101)I after regeneration. Such a high resistance to mercerization of the Valonia cellulose may be due to its larger crystallite size rather than the crystalline content.
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  • 188
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    Journal of Applied Polymer Science 11 (1967), S. 321-334 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Elastomer processing operations are discussed and classified as unit operations. The theory of nonlinear viscoelasticity is applied to processing unvulcanized amorphous rubber and the significance of the maximum relaxation time τm is emphasized.
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  • 189
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    Journal of Applied Polymer Science 11 (1967), S. 335-340 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Gel permeation chromatography was used to follow changes in the molecular weight distribution of a polyisobutene, initial Mv = 466,000, during degradation induced by sonic irradiation. Seven samples taken at times of 200-163,500 sec. were studied. In general, a steady decrease in molecular weight was observed, although a bimodal distribution was present after 20,000 sec. irradiation. Various measures of inhomogeneity, Mw/Mn, U, etc., were examined. The function, σn/Mw, where σn is the standard deviation of the number distribution, is considered as a measure of the relative distribution. It is shown to be almost constant throughout the degradation.
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  • 190
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    Journal of Applied Polymer Science 11 (1967), S. 2189-2200 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is proposed for predicting the exponent a of the Mark-Houwink equation, [η] = KMa. This method makes use of the solubility parameters of polymer and solvent.
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  • 191
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    Journal of Applied Polymer Science 11 (1967), S. 2227-2253 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The crosslinking efficiency of sulfur in the vulcanization of natural rubber in the presence of 2-mercaptobenzothiazole, zinc oxide, and lauric acid has been determined as a function of cure time, cure temperature, and lauric acid concentration. With a low concentration of lauric acid structurally complex networks are formed, which contain 11-19 combined sulfur atoms per chemical crosslink present. The complexity increases with time of vulcanization. With a high lauric acid concentration much simpler networks are formed, which become progressively more simple as reaction proceeds (6 network-combined sulfur atoms per chemical crosslink, decreasing to 2.4 with time). Increasing the cure temperature from 100 to 140°C. reduces the efficiency of crosslinking in both cases. The changes in efficiency are attributed to the influences of the reaction variables (in particular, the concentration of rubber-soluble complexes of the zinc laurate with zinc benzothiazolyl mercaptide) on the structure and subsequent reactions of initially formed polysulfidic crosslinks.
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  • 192
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Large variations in the microstructure of 1,4-polyisoprenes, from ca. 100% cis-trialkylethylene groups, as in natural rubber (NR), to ca. 40% cis- and 60% trans-trialkylethylene groups, as in an equilibrium-isomerized NR, have little influence on the overall chemistry of vulcanization of the polyisoprenes by a N-cyclohexylbenzothiazole-2-sulfenamide-accelerated sulfur system or by a dicumyl peroxide system. The peroxide crosslinks the equilibrium-isomerized NR more efficiently than it crosslinks NR; this is attributed to the sulfur dioxide, which is used to isomerize the NR, scavenging some of the nonrubber constituents in the NR, which are known to compete with the rubber hydrocarbon for reaction with free radicals from the peroxide. By comparison with NR vulcanizates, the corresponding equilibrium-isomerized NR vulcanizates have higher values of the C2 term of the Mooney-Rivlin stress-strain equation and higher χ (polymer-swelling liquid interaction parameter) values of the Flory-Huggins equation.
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  • 193
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    Journal of Applied Polymer Science 11 (1967), S. 2403-2415 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Stress-relaxation curves were obtained for ionomers containing different cations, per cents of ionization, and thermal treatments. Differences in the rheological behavior were found to depend more on the ionization level than on the ion. A recently proposed model for ionomers is discussed and found to be consistent with these results. In terms of this model the degree of ionization in the polymer acts as a regulator for the growth of small oriented lamellar (crystalline) regions. In the most general terms, the mechanical behavior and strength of ionomers appears dominated by the existence of “hard” regions interspersed among “soft” regions. In the polymers studied here there was some slight crystallinity; however, similar effects and explanations are probably suitable for amorphous “ionomers.” Toughness was also found in some completely amorphous carboxylcontaining copolymers without added ionic salts. The same explanation of “hard” regions interspersed among soft regions is also valid here. The “blocky” nature of the copolymerization may play a role in setting up this type of structure.
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  • 194
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    Journal of Applied Polymer Science 11 (1967), S. 2453-2465 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Cellulose esters which have a high degree of esterification are readily crystallizable by simple heat treatments. Such esters include cellulose triacetate, cellulose tripropionate, and mixed cellulose triesters. X-ray diffraction analysis shows distinct crystal patterns for these crystalline cellulose esters, and differential thermal analysis shows strong melting peaks. X-ray diffraction analysis of secondary cellulose esters, that is, esters having a substantially lower degree of esterification, shows very diffuse patterns which are only slightly indicative of crystalline structure. Differential thermal analysis, on the other hand, shows strong endothermic peaks which appear to indicate melting of crystalline material. Once melted, secondary cellulose esters cannot be recrystallized easily by simple heat treatments, but it has been found that treatment with certain solvents will induce crystallization. For instance, precipitation of secondary cellulose acetate from acetic acid gave a material which showed two melting peaks by differential thermal analysis, and precipitation from acetone gave a material which showed a single melting peak. A secondary mixed ester, cellulose acetate butyrate, precipitated from acetone had three melting peaks. The coincidence of two of the peak temperatures of this ester with those of the separate triesters of acetic and butyric acids indicated a block rather than a random substitution into the cellulose chain.
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  • 195
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    Journal of Applied Polymer Science 11 (1967), S. 1-22 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The solubility of ethylene was measured in water, water-tert-butyl alcohol, water-emulsifier, water-tert-butyl alcohol-emulsifier, and water-tert-butyl alcohol-emulsifier-polyethylene. The polymerization of ethylene in an emulsion system differs from that of other vinyl monomers in several ways: the rate of polymer formation is inversely proportional to the emulsifier concentration and to the number of particles, the molecular weight of the polymer increases as the particle size increases, the polymer contains bound emulsifier whose concentration depends inversely on the particle diameter. These peculiarities are attributed to a transfer reaction between polymer radicals and emulsifier adsorbed on the surface of the polymer particle. In the presence of a fatty-acid soap, the transfer probably occurs primarily at the carbon α to the carboxyl group.
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  • 196
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    Journal of Applied Polymer Science 11 (1967), S. 85-93 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The process of resole-type phenol-formaldehyde resins was studied by differential thermal analysis and infrared spectroscopy. It was shown that in neutral media the first reactions that occur are those between free phenol present in the resin and monosubstituted methylol phenol with free reactive positions on the benzene ring. The formation of methylene linkages is followed immediately by the condensation of methylol groups to give dibenzyl ether linkages. These are subsequently destroyed at about 210°C. It is believed that the entire curing process is governed by a free-radical mechanism. It is also shown that oxidation of the resin occurs slowly at room temperature and humidity.
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  • 197
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    Journal of Applied Polymer Science 11 (1967), S. 95-102 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of formation of dibenzyl ether linkages during cure of resole-type phenol-formaldehyde resins was studied by the use of differential thermal analysis and infrared spectroscopy. The activation energy was 21.6 kcal./mole by the Borchard and Daniels method gives and 18.6 kcal./mole by the Kissinger method. For the same process, infrared, which shows a rather good agreement between the two different methods. The heat of reaction, determined from the area under the DTA curve for the corresponding reaction, was found to be 20.2 cal./g.
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  • 198
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    Journal of Applied Polymer Science 11 (1967), S. 465-471 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyglycidyl esters of aromatic polycarboxylic acids were evaluated as adhesives for aluminum over the temperature range -453 to +400°F. The esters were cured either with amines or anhydrides. Cyclopentanetetracarboxylic acid dianhydride was found to be a superior curing agent and gave adhesives with tensile shear strengths in excess of 1000 psi at 400°F.
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  • 199
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    Journal of Applied Polymer Science 11 (1967), S. 527-551 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dielectric behavior of different polar high polymers at ultra-high frequencies has been investigated by means of a dielectrometer, suitably modified to permit measurements at different temperatures. Experimental measurements were made at about 9 × 109 cps over the temperature range of -150 to 200°C. for polyoxymethylene, polythiomethylene, poly(3,3′-chloromethyl)oxetane (Penton), polycarbonate of 4,4′-dioxydiphenyl-2,2′-propane (Makrolon), poly(vinyl alcohol), poly(vinyl acetate), poly(vinyl chloride), vinyl chloride-vinyl acetate copolymer, and two ABS plastics, type B (blend) and type G (graft). On comparing the dielectric behavior of the examined materials at ultra-high frequencies with the corresponding ones determined at low or at radiofrequencies, it is observed that, in the microwave region, all relaxation peaks, either connected with cooperative motions in main chain (primary processes) or with local motions in the backbone or in side chains (secondary processes), usually observed at lower frequencies, tend to disappear; the corresponding relaxation effects, however, manifest themselves through a progressive increase of losses with increasing temperature, which is particularly marked above the glass transition temperature Tg. The latter transition, in spite of the very high frequency, is easily distinguished, in most cases, by the sudden change of slope in the tan δ versus temperature curve which accompanies its onset. This is explained on the basis of the very wide distribution times of molecular relaxation processes in polymers and the increase in strength of the secondary relaxation effects, which is verified at Tg, as a consequence of the increased kinetic energy of macromolecules and of the larger free volume for orientation of side chains. Each case is discussed separately and the experimental results interpreted on the basis of the molecular structure and chain mobility of the examined polymers.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
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  • 200
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 605-608 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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