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  • Polymer and Materials Science  (8,218)
  • General Chemistry  (6,304)
  • 550 - Earth sciences
  • 1965-1969  (14,522)
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  • 1
    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: Three methods of measuring thermal oxidative stability of polypropylene have been compared. The oxygen absorption and the sealed tube tests give comparable results. The polymer lifetimes in circulating oven-aging tests differ significantly from those obtained by the first two methods. The oven-aging lifetime is aparently influenced to a large extent by the volatilization of the added stabilizer and of the oxidation products, the former decreases whereas the latter increases the polymer lifetime. The optimum composition of a synergistic stabilizer system was found to vary with the test method.
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  • 2
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 9 (1965), S. 3845-3850 
    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: During a program to evaluate the gel permeation chromatography (GPC) technique for measuring the molecular size distribution of polymers, three experimental epichlorohydrin-bisphenol A polymers were sent to Waters Associates for analysis with the commercially available instrument. The resulting distribution curves were used to calculate weight-average and number-average chain lengths of the samples. These values were found to give good straight-line correlations with weight-average and number-average molecular weights measured by absolute methods. Thus the GPC method gives meaningful information about the molecular size distribution of polymers which can be used to obtain rapid estimates of molecular weight.
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  • 3
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 9 (1965), S. 3863-3868 
    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 rate and extent of solution of polyvinylchloride in ester plasticizers has been measured using infrared spectroscopy. The measurement is based on shifts in the carbonyl stretching frequency of the ester linkage, similar to the familiar infrared solvent shifts commonly observed for low molecular weight materials. Double beam techniques were necessary to record the shifts. The intensity of the shifted band increases up to gelation and the rate of increase depends on the temperature of heating. The intensity of the shifted band is directly proportional to the concentration of polymer dissolved in the plasticizer and can be used to measure this concentration at any time during the gelation process. It is estimated that from 17 to 22 per cent of the polymer was dissolved at the gel point after heating at 65°C. and that about 29 per cent of the polymer was dissolved at the gel point after heating at 75°C., for the plastisols used in this study.
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  • 4
    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 stability characteristics of three rigid urethane foams prepared from various formulations, to give a wide range of molecular structure, were investigated by means of TGA, DTA, and long-term heat aging. Compressive strength values over a temperature range of -73°C to +232°C were also determined for these foams. Based on all tests performed, a toluene diisocyanate foam displayed the poorest thermal stability characteristics of the three foams studied. A combination toluene diisocyanate-polymethylene polyphenylisocyanate foam showed intermediate elevated temperature properties, whereas, a foam employing only polymethylene polyphenylisocyanate demonstrated the best over-all high temperature stability.
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  • 5
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    Journal of Applied Polymer Science 9 (1965), S. 3869-3885 
    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: Rates of decrease in crystallinity, as measured by x-ray crystallinity index, have been followed throughout periodate oxidations of cotton cellulose and formaldehyde-treated cotton celluloses. Depending upon the conditions under which the agent was introduced, a low level of formaldehyde crosslinks exerted small or large retardation on the rate of decrease of crystallinity index. The extents of decrystallization per unit of oxidation of cotton and crosslinked cotton celluloses are substantially smaller in the initial phase of oxidation than in the later stage, indicative of preferential oxidative attack in the early stage on chain segments of predominantly noncrystalline regions. Relative to unmodified cotton, crosslinked cotton celluloses are characterized by more extensive decrystallization per unit of oxidation in the early phase of oxidative attack (to approx. 40%). From these data, supplemented by electron micrographs and solubilities in cupriethylenediamine hydroxide, uniformity of distribution of crosslinks is shown to increase in this series of formaldehyde-modified cotton celluloses (at the same level of agent) in the order: form D cotton (nonaqueous treatment) 〈 form W cotton (aqueous treatment) 〈 form V cotton (vapor treatment). Effectiveness of crosslinking (i. e., composite of number of linkages, ratio of intermolecular to intramolecular bonds, low degree of polymerization in crosslink) is indicated to increase from form W to form D to form V cotton.
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  • 6
    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-strain curves at various temperatures and secant modulus vs. temperature curves were used to investigate the differences that exist between peroxide crosslinked polyethylene, and vulcanized rubber. A series of hypotheses in terms of crosslinking density and crystallinity is advanced to help visualize the differences between crosslinked polyethylene and cured rubber. The same techniques were used to investigate the nature of crosslinked ethylene-ethyl acrylate copolymers. These copolymers, being more flexible than polyethylene, appear similar to “mechanical rubber,” particularly after crosslinking. Recent experiments, however, indicate that profound differences exist. The performance of crosslinked polyethylene and of ethylene copolymers at elevated temperatures depends on crosslinking density, while at lower temperatures it is dominated by polyethylene crystalline morphology. This latter factor makes crosslinked polyethylene at ambient temperature a completely different product from vulcanized rubber. It also means that a crosslinked polyethylene will have lower crosslinking density than most rubber compositions of equivalent room temperature stiffness. A good indication of crosslinking density of crystalline polyolefins may be obtained by measuring mechanical properties such as modulus at elevated temperatures. Use of reactive co-agents is effective in raising crosslinking density to the point where fairly good elevated temperature properties are obtained without increasing the room temperature rigidity.
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  • 7
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    Journal of Applied Polymer Science 9 (1965), S. 4025-4028 
    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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  • 8
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    Journal of Applied Polymer Science 9 (1965), S. 3963-4001 
    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 specific refractive index increments of 158 natural and synthetic polymers and copolymers in pure and mixed solvents have been collated. Wherever possible the temperature and wavelength (generally 436 and/or 546mμ) are quoted.
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  • 9
    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 comprehensive study of the performance of various types of carbon black in polyethylene has been made. The physical and chemical properties of carbon blacks are discussed, and the effectiveness of various blacks as ultraviolet screening agents for polyethylene is assessed. It is seen as a first approximation that primary particle size is the property of the carbon black which largely governs the weatherability of a compound. The data suggest that this is due to that fact that the degree of ultraviolet protection is dependent on the presence of submicroscopic aggregates and their distribution throughout the polymer mass. It is proposed that the aggregate size and distribution are largely controlled by the surface energy arising from the dimensions of the primary particles. Studies of carbon black-antioxidant systems gave results which were in agreement with those of Hawkins et al., who found that carbon blacks having a polar surface exhibit a synergistic behavior with organosulfur type antioxidant, greatly increasing the time required to absorb a given amount of oxygen or undergo thermal degradation. The present study shows that use of antioxidants also contributes to the ability of polyethylene compounds to resist accelerated aging. Outdoor aging of the same compounds are in progress, but more time is required to see if antioxidants are helpful in the manner indicated by the accelerated weathering studies. The effect of carbon blacks on the mechanical properties of polyethylene is discussed, and data are presented to show that higher loadings of carbon black than normally used for ultraviolet protection greatly increase the tensile yield (stress at draw point) at relatively fast rates of applied stress. It is suggested that the use of moderately high concentrations of carbon black would enhance the performance of polyethylene in applications such as pipe which often fails under rapidly applied stress.
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  • 10
    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: With a view to permanently incorporating ultraviolet stabilizing moieties into polymer systems, monomers containing the phenyl salicylate structure have been prepared and polymerized. Phenyl 5-acryloxymethylsalicylate and phenyl 5-methacryloxymethyl-salicylate were prepared by the chloromethylation of phenyl salicylate and subsequent reaction with sodium acrylate or methacrylate. Homopolymers and copolymers of the methacryloxymethyl monomer were prepared and studied. The ultraviolet spectra of the chloromethyl derivative, the monomers, and the homopolymers were essentially similar to that of the starting material, phenyl salicylate. Copolymers of the ultraviolet-absorbing monomers (2%) with vinyl acetate, vinylidene chloride, and vinyl chloride were prepared. The ultraviolet stability of these copolymers was then compared to that of an unstabilized control series and a series containing phenyl salicylate. While there were some differences in the behavior of the copolymerized absorber it was at least as effective as phenyl salicylate in stabilizing the polymers.
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  • 11
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    Journal of Applied Polymer Science 9 (1965), S. 941-946 
    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: Electrolyte sorption of a rubber-based cation-exchange membrane has been studied for two samples of different rubber contents. The sorption behavior is discussed in terms of the capillary volume between rubber and the resin, and an explanation is provided for the difference in the behavior of the two samples.
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  • 12
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    Journal of Applied Polymer Science 10 (1966), S. 291-301 
    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 investigation showed, as did an earlier investigation, that the adhesives tested exhibit greater resistance to rapidly applied stresses than they do to slower or gradually applied stresses. Also, the adhesives were shown to lose strength with test temperature whether tested rapidly or slowly. Within a region bounded approximately by a high-temperature second-order transition point (the ASTM heat distortion temperature) and a low-temperature second-order transition point, the test data fits an Arrhenius-type exponential equation, S = AeE/RT, where S is the stress in the joint at failure and the other terms have their usual significance. Energies calculated from this expression are lower for dynamic (fast) than for static (slower) rates of testing. Further, it was shown that little change in bond strength occurs until time to failure is below 100 msec. Plots of stress versus 1/T for a series of test times show a decided discontinuity at 1/T = 0.0039 or -16°C.
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  • 13
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    Journal of Applied Polymer Science 10 (1966), S. 303-313 
    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 property changes of Epon 828 crosslinked by either diethylenetriamine or m-phenylenediamine at several temperatures have been studied by two in situ techniques. The mechanical property changes were followed by continuously monitoring the changes in the fundamental frequency of vibration during cure of a resin-coated substrate acting as a cantilever reed. The disappearance of the reactive epoxy group was followed in situ by continuously monitoring the absorbance of the infrared epoxide band at 915 cm.-1. Correlation of the two techniques was accomplished by normalizing both the mechanical property and infrared data. The apparent energy of activation was calculated to be 10.4 and 11.4 kcal. /mole, respectively, for the m-phenylenediamine and diethylenetriamine systems by the mechanical technique, and 11.0 kcal./mole for the m-phenylenediamine crosslinked system by the infrared technique.
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  • 14
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    Journal of Applied Polymer Science 10 (1966), S. 353-359 
    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 explicit expression is derived for the weight distribution function of polymer molecules in a photodegraded film. A most probable weight distribution of linear molecules is assumed initially present; normally incident, monochromatic light obeying a single Beer-Lambert absorption relation is the photolyzing radiation. The dependence of the weight distribution upon the film's optical thickness and the integrated incident light flux is illustrated by curves computed according to the derived functions. Predicted gel permeation chromatograms are indicated.
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  • 15
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    Journal of Applied Polymer Science 10 (1966), S. 361-374 
    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 role of the capillary end correction in flow analysis of molten low-density polyethylenes has been analyzed. In spite of limitations of accuracy a quantitative approach has been undertaken. The results are much more complicated than predicted by Bagley in his early reports. The elastic component of the end correction is controlled by shear stress and shear modulus. The latter is affected by the size of the subchain between entangles, Me, and by the degree of long-chain branches. Both are eventually dependent on the length of the chain, i.e., its molecular weight. In addition shear stress and temperature affect the process of disentanglement. Capillary end correction increases with increasing molecular weight and shear stress and with decreasing temperature. The available analysis of branching is still in controversy, and therefore no numerical parameters are yet proposed. A consistent theory of the response of entanglement couplings to shear forces and temperature is evaluated.
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  • 16
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    Journal of Applied Polymer Science 10 (1966), S. 437-441 
    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: Changes in the stress-strain curve for paper undergoing cyclic loading have been studied as a function of moisture content. It has been found that the extensional stiffness of the paper progressively decreases at both low and high moisture levels but progressively increases at intermediate moisture levels. The moisture content at which the transition from decreasing to increasing stiffness occurs (when passing from low to intermediate moisture content) has been determined and for the particular paper used in these experiments has been shown to correspond to a relative humidity of approximately 60%. It is postulated that at low and high moisture levels, conditions are not favorable for interfiber bond re-formation, whereas conditions are favorable for such reformation at intermediate moisture levels.
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  • 17
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    Journal of Applied Polymer Science 10 (1966), S. 481-489 
    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: Apparent viscosities of linear polyethylene melts may be simply related to molecular weight at various shear stresses. One gets constant slopes on a log-log scale with higher critical M̄w at higher shear stresses. The validity of Ferry's equation and the dependence of its coefficients are extensively analyzed.
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  • 18
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    Journal of Applied Polymer Science 10 (1966), S. 491-509 
    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: Three different styrene-butadiene, gum rubbers were exposed to γ-radiation doses ranging from 0 to 200 Mrad. The crosslink densities, hardness, and the dynamic mechanical properties were evaluated. All specimens increased in hardness and crosslink density during radiation. This was reflected in an increased storage modulus, broadened loss tangent maximum, and increased relaxation spectrum. The dynamic data are presented in master curves which were developed by using the WLF equation.
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  • 19
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    Journal of Applied Polymer Science 10 (1966), S. 601-617 
    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: Tires containing nylon tire cord exhibit a temporary deformation upon standing under load. The delayed recovery from this deformation, due to the fact that the yield point of nylon is exceeded under normal inflation pressures, results in the phenomenon of “flatspotting.” Previous attempts to improve the viscoelastic characteristics of nylon by crosslinking have been discouraging on account of the general degradation of properties caused by the treatment. It has now been found that short, vapor-phase treatments with diisocyanates, particularly tolylene diisocyanate, produce nylon 6 of greatly improved flatspotting resistance, without undersirable side effects. The development of this procedure, the evaluation methods employed, and the proposed mechanism are discussed.
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  • 20
    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 changes in nylon 66 fiber structure and properties which take place during drawing and aqueous phenol treatments were studied by means of measurements of length, birefringence, density, moisture regain, x-ray diffraction, stress-strain behavior, and sound velocity. Drawing was found to establish molecular orientation along the fiber axis predominantly in the early stages, whereas the development of lateral order occured primarily after a certain level of orientation had been achieved. Treatments in aqueous phenol solutions caused longitudinal contractions which depended on phenol concentration (1-5%), draw ratio (1-6), and the tension on the fiber during the treatment. The treatments resulted in an increase in the lateral order, decrease in orientation and corresponding changes in mechanical properties. Moisture regain was inversely related with density for the untreated fibers of various draw ratios, but the relationship became complex after treatments in phenol. The data are interpreted in terms of changes in the lateral order distributions, which permits an increase in the fibers' sorptive capacity despite an increase in the mean lateral order.
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  • 21
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    Journal of Applied Polymer Science 9 (1965), S. 1213-1225 
    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 dynamic mechanical and tensile deformation and ultimate properties are reported for two epoxy resins in the temperature range, from the glass transition Tg to Tg + 100°C. The epoxy resins are stoichiometrically reacted diglycidyl ether of bisphenol A with an aromatic (Tg = 115°C.) and an aliphatic (Tg = 47°C.) diamine curing agent. Dynamic measurements were conducted on a rotating cantilever beam instrument over the frequency range from 0.01-100 cycles/sec. Tensile deformation and fracture characterization were obtained by constant rate of strain measurement at strain rates of 0.000445-0.445 sec. -1. Both dynamic and tensile modulus data as well as ultimate stress and strain response superimpose by time and temperature reduction to form unified “master curves.” The time or frequency shift factor aT for both dynamic and tensile deformation and fracture properties follow the predictions of the familiar Williams-Landel-Ferry equation. The rheological and fracture master curves are discussed in terms of both monomer composition and equilibrium response of the crosslinked network. The regions of maximum dynamic dispersion are associated with rubbery state high elasticity tensile response for these epoxies and the magnitude of responses correlated.
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  • 22
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    Journal of Applied Polymer Science 9 (1965), S. 1233-1251 
    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: Investigations of the dynamic cut growth behavior of vulcanized rubbers indicate that there is a minimum tearing energy at which mechanical rupture of chains occurs. The limiting value is characteristic of each vulcanizate, but is in the region of 0.05 kg./cm. The mechanical fatigue limit, below which the number of cycles to failure increases rapidly, is accurately predicted from this critical tearing energy. Characteristics of cut growth at low tearing energies, and effects of polymer, vulcanizing system, oxygen, and fillers on the critical tearing energy and fatigue limit are discussed.
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  • 23
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    Journal of Applied Polymer Science 9 (1965), S. 1253-1259 
    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: Studies have been made of the oxidation of styrene popcorn polymer that was grown on butadiene popcorn seed. It was found that the solubility of the polymer increased after oxidation. This solubility was studied as a function of both temperature and butadiene content of the polymer. Oxidation of the styrene-on-butadiene popcorn occurs at the carbon atoms alpha to a double bond in the butadiene portion of the polymer. This is followed by scission of the structure and the separation of linear atactic soluble polystyrene chains.
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  • 24
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    Journal of Applied Polymer Science 9 (1965), S. 1291-1297 
    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 quantitative theory of free radical mechanisms in emulsion polymerizations is reexamined. It is suggested that existing descriptions are not entirely consistent with physically realizable situations. The proposed modifications result in a closer resemblance to homogeneous systems. Explicit expressions for the distribution of radicals are also given. The importance of interphase transfer is emphasized.
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  • 25
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    Journal of Applied Polymer Science 9 (1965), S. 1273-1283 
    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 model equation derived for the viscosity-average degree of polymerization (P̄v) for the incremental addition of modifiers, P̄v = K{(exp{arx1} - 1) + [2/(2 + exp {x1r})]a(exp{arx2} - exp{arx1})}1/a indicates a minimum should occur in a curve of P̄v versus conversion at which the increments are added, x1. Incremental addition of commercial tert-dodecyl mercaptan in the laboratory to SBR recipes at 5°C. showed effects contrary to those predicted by the model equation, but incremental addition experiments with tert-nonyl mercaptans resulted in a minimum in viscosity versus x1 curves, changed the molecular weight distribution, and required 34 wt.-% less mercaptan than did the tert-dodecyl mercaptan control (all the tert-dodecyl mercaptan added initially). Incremental addition of tert-nonylmercaptan in pilot plant 20-gal. autoclave reactors gave essentially the same results found in the laboratory bottle experiments. The stress-strain and mixing properties of the incrementally modified polymer and the tert-dodecyl mercaptanmodified control were essentially the same within experimental error. Conditions required for successful application of the incremental modifier technique are given.
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  • 26
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    Journal of Applied Polymer Science 9 (1965), S. 1323-1340 
    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: Terpolymers from 1,3-butadiene, styrene, and vinylpyridine are important as rubbers, and, in latex form, as components of rubber-to-fabric adhesives. Three monomer mixtures having the approximate weight composition butadiene/styrene/2-methyl-5-vinylpyridine 70/15/15, 25/48/27, and 38.5/49/12.5 have been emulsion-polymerized at 30°C., and the terpolymer composition as a function of the conversion has been studied. The six monomer reactivity ratios have been determined by binary copolymerizations at 30°C. and checked by low conversion bulk terpolymerizations. Average and instantaneous composition-conversion curves have been calculated, on the assumption of a constant reaction volume, by numerical integration of the terpolymerization equations on electronic computer. Details, of general applicability, for calculations are given. The experimental results of the emulsion terpolymerizations fit satisfactorily the calculated curves over a wide range of conversions.
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    Journal of Applied Polymer Science 9 (1965), S. 1363-1366 
    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 radiation-induced vulcanization of cis-polybutadiene (Europrene Cis, 92% cis-configuration) was investigated. The crosslinking density of irradiated rubber was determined by two methods: equilibrium swelling and equilibrium compression modulus. The inhibition and acceleration of radiation-induced crosslinking by addition to Europrene Cis of sulfur, Thiurame, Elastopar, Arubrene, paraffin oil, or barium sulfate was studied. The chemical resistance of radiation vulcanizates to 10% nitric acid was determined.
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  • 28
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    Journal of Applied Polymer Science 9 (1965), S. 1419-1429 
    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: Acetal copolymers prepared from trioxane and ethylene oxide consist of polyoxymethylene segments with oxyethylene units distributed in the chain. These oxyethylene units profoundly affect the thermal and chemical behavior of the polymer. The presence of the oxyethylene units renders the copolymer amenable to thermal or base hydrolytic treatment which results in a final product with stable endgroups. The copolymers so obtained are significantly more stable, thermally and chemically, than acetylated polyoxymethylene homopolymer.
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  • 29
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    Journal of Applied Polymer Science 9 (1965), S. 1431-1435 
    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: Efforts to prepare 1,6-dicyano-2,4-hexadiyne resulted in the formation of insoluble, chemically inert, high-melting “brick dust” type polymeric materials. Similar appearing products arose from the dihalo-, ditosyl-, and dihydroxy- hexadiyne derivatives as well as propargyl halide starting materials. It appears that diacetylenic diols and their propargylic precursors undergo direct nitrilation.
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  • 30
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    Journal of Applied Polymer Science 9 (1965), S. 1487-1497 
    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 new type dilatometer has been described which will automatically record the volume changes which occur during the entire course of polymerization reactions. Experiments have shown that the weight per cent polymer in a monomer solution is more accurately described as a function of additive densities of monomer and polymer than of additive volumes of monomer and polymer. The operation of the dilatometer, the relation of the observed volume changes to monomer conversion to polymer, and the possible errors involved in these type measurements have been discussed. The apparatus has been used to obtain rate curves for the polymerization of both linear and crosslinked vinyl monomer compositions over the entire course of polymerization, despite the early formation of a firm crosslinked gel structure in the latter case.
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  • 31
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    Journal of Applied Polymer Science 10 (1966), S. 1011-1026 
    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: When an uncompounded elastomer is processed on a two-roll mill, four different regions of mechanical behavior are observed, depending upon the temperature and the severity of the nip deformation. this behavior is observed on materials with a wide variety in chemical composition, through the severity varies. The flow at high temperatures is typical of melt or polymer solution behavior. At lower temperatures unstable flow and elastic solidike regions are observed. By presuming the elastomer to be an isotropicviscoelastic medium, the stress and velocity fields were computed in the polymer melt region. The unstable regime was found to correspond to a critical value of the ratio of viscoelastic to viscous forces. The mathematical analysis, done interms of the Green-Rivlin-Noll theory of viscoelastic media, extends earlier studies of deformation in this geometry by Gaskell and Bergen.
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  • 32
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    Journal of Applied Polymer Science 10 (1966), S. 1111-1119 
    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 of data interpretation known as nonlinear least squares has recently been applied by several authors to the study of polymeric materials. Nagler has used a modified method proposed by Blizzard and Jirka and has concluded that the method is impractical because it requires excessive computer time. It is shown that the difficulties Nagler encountered are inherent in Blizzard and Jirka's method, but not in the basic method. Three steps are outlined to minimize computer time, and a summary of successful applications is presented.
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  • 33
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    Journal of Applied Polymer Science 10 (1966), S. 1171-1183 
    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 stability and trace volatiles content of polymers can be determined rapidly and conveniently by using a hot-filament pyrolyzer for heating the sample. The filament unit, of a type employed for pyrolysis-GLC analysis, consists of a platinum coil with an attached platinum/platinum-rhodium thermocouple for measuring the sample temperature. As the sample is heated the volatile products are monitored directly with a flame ionization detector, a dual recorder being used to chart both temperature and volatiles yield. At any stage of heating the products are analyzed, if desired, with a suitable GLC column. Thermal stability measurements of several polymers were generally consistent with results by conventional thermogravimetric analysis. Advantages of the method are high sensitivity for detection of low decomposition rates, speed of the temperature adjustment, simplicity of the apparatus, and small sample requirement.
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  • 34
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    Journal of Applied Polymer Science 9 (1965), S. 333-349 
    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 adherence of the diffusion of (cationic) dyes in polyacrylonitrile fibers to Fick's law with a constant diffusion coefficient is discussed at the hand of diverse experiments. More specifically, an attempt is made to account for apparently abnormal radial color intensity distributions. There is no evidence for polymer plasticization by the dye. The (linear axial) thermal expansion, glass transition temperature, disorienting shrinkage temperature, and other properties are not appreciably affected by saturating the fiber with dye. The evidence from both sorption and penetration measurements indicate concentration-independent diffusion from a limited number of specific (sulfonate) surface sites. The behavior appears to be so simple that saturation values can be measured from the sorption curves. It is shown that, for diluents with the molecular properties of dyes, a free volume model of dye diffusion predicts the absence of plasticization effects in dyeing systems in general. Replacement of the concentration in the diffusion equation by an activity function, θ/(1 - θ), where θ is the fraction of sites occupied by dye, suggested for the analogous case of anionic dyes on nylon is considered and shown not to be justified on a thermodynamic basis. A similar function can be derived on reasonable kinetic grounds, but is not borne out by the detailed results.
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    Journal of Applied Polymer Science 9 (1965), S. 1227-1232 
    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 the use of x-ray diffraction techniques a method is proposed for the measurement of the “smectic” content (interpreted here as material of intermediate order) of undrawn polypropylene filaments. The method involves two estimates of crystallinity by x-ray methods. One is considered to measure the amount of diffraction from the normal crystalline monoclinic lattice and the other the total amount of diffraction from crystalline, “smectic” and noncrystalline material. By separation of these various quantities the amount of “smectic” polypropylene can be deduced. It was found by this technique that the “smectic” content of quenched polypropylene samples decreased from 40°C. onward and approached zero at about 85°C.
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    Journal of Applied Polymer Science 9 (1965), S. 1261-1271 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The polymerization of styrene on neutral mineral surfaces has been studied. It has been shown that the polymerization has characteristics expected for both a radical and cationic reaction, and a mechanism involving a radical-carbonium ion is proposed to explain this evidence. A range of mineral catalysts have been investigated and a tentative theory proposed to relate the variation in activity with catalyst structure. Experiments have also been carried out to define the specific portion of the mineral surface responsible for the catalyst activity.
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    Journal of Applied Polymer Science 9 (1965), S. 1285-1290 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Parlodion membranes 95 to 500 A. thick have been prepared on a glass surface by dipping a clean glass plate into the Parlodion solution and subsequently evaporating the solvent under controlled conditions by keeping the glass plate vertical in a metallic frame and covered with an inverted beaker. The membrane may be floated off on to an aqueous surface. Capacitance measurement established the thickness of the membrane. Electrical resistance and isothermal diffusion potentials arising across them when they separate different salt solutions have also been measured at room temperature.
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  • 38
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    Journal of Applied Polymer Science 9 (1965), S. 1299-1321 
    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: cis-1,4-Polybutadiene and trans-1,4-polybutadiene were mixed at the ratio in weight of 100/0, 75/25, 50/50, 25/75 and 0/100, and various problems related to the mixing were studied. The mixing was carried out by the three methods, i.e., (1) by rolling, (2) by filler batch polymer, and (3) by coprecipitation of the solution. For the mixed compound and vulcanized rubber, such characteristics as the viscosity of the solution, the Mooney viscosity, x-ray diffraction, infrared spectra phase separation of the solution, tensile strength, and the swelling ratio in benzene were observed. No marked difference in the state of mixing was noted, regardless of the method of mixing. However, the mixing of filler batch polymer was accomplished more easily than by the rolling method. A 50/50 blend rubber was microheterogeneous and contained particles about 0.5 μ in length, but these did not affect the crystallization, as judged from the observation of the state of dispersion, by means of electron microscopy, x-ray diffraction, and infrared analysis. The trans-4 polymer, vulcanized at a much slower rate than Cis-4. This was revealed by comparing infrared spectra of extracts obtained from the unvulcanized portion after various vulcanization times. The Cis-4 vulcanizate did not show any crystalline pattern even at 550% elongation.
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  • 39
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    Notes: Diffusion and distribution coefficients of water and sodium chloride have been measured in cellulose acetate osmotic membranes. These coefficients have been found to vary with the degree of acetylation of the cellulose ester. The diffusion coefficient of water varies from 5.7 × 10-6 to 1.3 × 10-6 cm.2/sec., and the diffusion coefficient of salt varies from 2.9 × 10-8 to 3.9 × 10-11 as the acetyl content is increased from 33.6 to 43.2 wt.-%. A homogeneous diffusion model is proposed which describes the observations in terms of Fick's law.
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  • 40
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    Journal of Applied Polymer Science 9 (1965), S. 1367-1384 
    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 method of differential thermal analysis has been applied to the study of thermal effects accompanying exothermic vulcanization reaction in hard rubber compounds accelerated with common rubber accelerators. Exothermic reaction was found to start at about 1% sulfur, in the case of CBS-accelerated compound which increases linearly up to 32% and then decreases, probably due to predominance of a dehydrogenation reaction. 68/32 Rubber-sulfur compounds containing increasing amounts of combined sulfur evolve decreasing quantity of heat and a plot of ΔH vs. combined sulfur of the precured compounds shows three stages of reaction. Accelerators were found not to affect the heat of reaction of the compounds to a great extent except in the special cases of those containing MBT and ZDC. The beneficial effect of certain accelerators is to be traced in the lowering of initiation temperatures and a decrease of slope values whereby the reaction becomes more regulated and spread out. Increase of concentration of accelerators (CBS and TMT) was found to have little effect.
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  • 41
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    Journal of Applied Polymer Science 9 (1965), S. 1395-1417 
    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 reaction of lithium aluminum hydride forming mercaptan with disfulfides and mercaptan as well as hydrogen sulfide with polysulfides has been applied in order to characterize the structure of the crosslinks in the case of unaccelerated vulcanization of natural rubber with sulfur. The mercaptans formed were determined amperometrically, and the hydrogen sulfide was determined as cadmium sulfide. These measurements, coupled with the estimation of total crosslinks as measured by swelling, provide valuable information as to the distribution f different crosslinks (monosulfide, polysulfide, cyclic structures, etc.) in the vulcanizate. When extended to compounds of different sulfur concentrations (2.92-33.9%) these studies show how the distribution of different linkages changes with sulfur concentration from compositions corresponding to soft rubber to those corresponding to hard rubber. The present study provides conclusive evidence that the long polysulfidic crosslinks first formed during vulcanization decrease in chain length as vulcanization progresses. Polysulfides also increase with the increasing sulfur content in the stock except in the range 6-10%. Monosulfidic crosslinks increase with increasing sulfur in the stock. In contrast to accelerated vulcanization, a high proportion of combined sulfur was found to be present in cyclic structures, and this increases with temperature of curing. These findings tally with the results of the earlier workers and have been explained with the present day ideas of the vulcanization reaction. Inaccuracies in the measurements and inherent limitations of the method were discussed.
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  • 42
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    Notes: It was found that poly-β-vinylnaphthalene and poly(ethylene oxide) (54:46% by weight) form homogeneous blends or graft copolymers when prepared under conditions which inhibit the crystallization of poly(ethylene oxide). Such preparations can be obtained from solutions in a good solvent for both components, either by precipitation procedures which lead to coacervation rather than fractionation, or by freeze-drying. Preparations containing more than 46 wt.-% poly(ethylene oxide) were characterized by modulus versus temperature curves exhibiting a minimum at about 60°C. This behavior was interpreted as due to microphase separation taking place with increasing temperature, a process which becomes irreversible above 120°C. A graft copolymer having the 54:46 composition was rubbery at room temperature, and in contrast to polyblends did not exhibit the poly-β-vinylnaphthalene glass transition at 138°C. The marked difference in behavior between polyblends and graft copolymers is due to the fact that in the latter irreversible microphase separation cannot take place. The above described properties seem to be peculiar to poly-β-vinylnaphthalene. Similar properties could not be reproduced in preparations of poly(ethylene oxide) with polystyrene, poly-4-vinylbiphenyl, or polyacenaphthylene. These preparations exhibited a behavior characteristic of mixtures of two incompatible polymers.
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    Journal of Applied Polymer Science 9 (1965), S. 545-552 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The rates of adsorption of PAM's were measured on calcium phosphate at various intensities of agitation. Vigorous mechanical stirring promotes the adsorption by degrading the floccules, thus providing new surfaces available for further adsorption of polymers. The rising parts of the rate curves correspond to the breaking up of flocs or “deflocculation” by the applied mechanical stirring. The flat portions of the curves in the high stirring time range indicate complete redispersion; no further surfaces are available for the adsorption of polymer flocculants. The effect of the intensity of agitation upon adsorption was investigated. Increasing the number of revolutions of the stirrer causes the adsorption curves to rise more sharply. This suggests that the deflocculation also becomes more rapid. At equimolar initial concentrations the rates of adsorption and deflocculation decrease with increasing molecular weight.
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  • 44
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    Journal of Applied Polymer Science 9 (1965), S. 561-568 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The dynamic behavior at low frequencies of Penton (chlorinated polyether) which displays nonlinear response is described in terms of a free energy function and a dissipated energy function. The variation of the energy functions with frequency and magnitude of stress is determined experimentally from hysteresis tests. The dynamic properties of the material are expressed in terms of storage and loss modulus functions. In addition the dynamic behavior of the material at low frequencies is predicted from uniaxial static creep properties, using a modified superposition principle.
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    Journal of Applied Polymer Science 10 (1966), S. 1973-1974 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 46
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    Journal of Applied Polymer Science 10 (1966), S. 1949-1971 
    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 cumulative extension cycling behavior is a combination of the effects of elastic recovery, viscoelasticity, and fatigue. The purpose of this research was to examine the elastic recovery aspects of the behavior. A model behavior idealized to include only elastic recovery was assumed and a computer program written to simulate cumulative extension cycling behavior based upon this idealized model. Tests were performed with an apparatus which removed the sample's slack after each cycle. A comparison of the experimental and computed results yielded an improved understanding of the elastic recovery aspects of the cumulative extension cycling behavior.
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  • 47
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    Journal of Applied Polymer Science 11 (1967), S. 73-84 
    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: Complexes of aluminum alkyls with Lewis bases catalyze the polymerization of vinyl chloride. Triethylaluminum is most effective, but other compounds of type R3Al, R2AlCl, R2AlH, and LiAIR4 are operable. Dialkylmagnesiums are active, but Grignard reagents, as well as a number of other metal alkyls are inactive. Among Lewis bases, tetrahydrofuran (THF) and tetrahydropyran give the best yields of poly(vinyl chloride). Oxygen bases, such as ethers and esters, are more effective than nitrogen bases, e.g., tertiary amines. Cyclic compounds are better than acyclic ones. The polymerization occurs in a variety of hydrocarbon, chlorinated hydrocarbon, or ether solvents, but especially well in CCl4. Radical polymerization is probably initiated through the reaction R3Al:Base + CCl4 → R2AlCl: Base + R + Cl3C., to form trichloromethyl radical.
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  • 48
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    Journal of Applied Polymer Science 11 (1967), S. 57-71 
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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: Copolymerization of unsaturated polyester with styrene in water-in-oil (W/O) type emulsion was carried out with the use of various basic compounds as emulsifiers. It was found that a stable, gellike W/O type emulsion of unsaturated polyester resin is formed only when pKa's of the bases are above 6 and their concentrations are higher than some critical value. In these conditions, water can be dispersed in emulsion up to 900% to the resin. By polymerization, the stable W/O type emulsion is transformed to a white solid copolymer which is dry to the touch and which contains 90-95% of initially added water. It was confirmed that the basic compounds react with the carboxylic group of the polyester to form at the water-resin interface polyester salts, which act as true emulsifying agents. The stabilization mechanism of the emulsion at various concentrations of the polyester salt was investigated, mainly by microscopic observations, and an interpretation of the critical value of emulsifier concentration is proposed.
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    Journal of Applied Polymer Science 11 (1967), S. 133-136 
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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: Certain homopolymer-polyol mixtures, after treatment with a free-radical generating agent or ionizing radiation, will produce polyurethane elastomers of nearly twice the stiffness and tensile properties compared to control elastomers made with untreated mixtures. Specific examples of these mixtures include the homopolymers of acrylonitrile and vinyl chloride with a poly(oxypropyl) triol of about 3000 molecular weight as the polyol in each case. The marked improvement in the stiffness and tensile properties of elastomers made with the treated mixtures over those of the untreated controls indicates a grafting process occurring between the polyol and homopolymer upon the generation of free radicals. In the present work, grafting could occur by a chain-transfer hydrogen-abstraction mechanism, whereby a free-radical site is generated on both the homopolymer and polyol chains. Coupling of these two free-radical sites would thus result in the establishment of a polymer-polyol graft bond.
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    Journal of Applied Polymer Science 11 (1967), S. 115-126 
    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 vinyl monomers, mainly methyl methacrylate, in reduced, successively alkylated, or KCN-Treated wool fibers was performed in the redox LiBr-persulfate system without homopolymer. The reduction gives a striking effect in promoting the graft copolymerization. Methylation or ethylene recrosslinking of the reduced wool, especially the former, decreases the graft-on remarkably. By the KCN treatment in which the conversion of disulfide to lanthionine bonds occurs, the grafting is decreased in the bromide-persulfate system but promoted in the system with persulfate alone. Methylation or KCN treatment of wool as well as reduction brings about a great increase in the absorption of persulfate. The grafting of the lanthionine-containing wool in the redox system accompanied by the liberation of bromine might be retarded by the pronounced bromination of monomers over the inhibiting of homopolymerization, because the lanthionine bonds are more stable to bromine than the disulfide bonds. In general, disulfide bonds and the other easily oxidized components of wool may perhaps play an important role in regulating the bromination of monomers and in the graft copolymerization without homopolymer. The molecular weight of graft polymer is decreased distinctly with increasing extent of reduction of wool. From these results, the thiol groups on wool are considered to give predominantly graft centers by the radicalotropy from SO4-·, OH·, and/or Br·.
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  • 51
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    Journal of Applied Polymer Science 11 (1967), S. 153-153 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 52
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    Journal of Applied Polymer Science 9 (1965), S. 1797-1805 
    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: Formulas and operating conditions for the emulsion polymerization of ethylene are described. Stable latex products were obtained with a variety of anionic and nonionic emulsifiers, but for the majority of the work fatty acids or polyethoxylated alkyl phenols were used. Potassium persulfate was a satisfactory initiator at concentrations of 0.05-0.50 part per 100 parts of aqueous medium. Substitution of up to 15% of the water with tert-butyl alcohol increased the latex particle size and the molecular weight of the polymer. Pressures of 3000-5000 psig and temperatures in the range of 80-100°C. provided practical polymerization rates and stable latex products that could be concentrated by evaporation to 40-50% solids. The concentrated products were fluid and stable during storage for one year or more. Polymer isolated from the latexes exhibited a tensile strength of 1100-1400 psi, an elongation of 30-50%, and a Shore D hardness of 40-45.
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  • 53
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A study has been conducted of the kinetics of the reactions of primary and secondary alcohols with phenyl isocyanate in the presence of metal catalysts. It has been determined that the type and concentration of metal catalyst, the structure of the alcohols, and the type of solvent play an important role in the reaction rates and ratios of rate constants. Catalysis by lead naphthenate increased the reaction rates of 2-methoxy-l-propanol and 1-methoxy-2-propanol more than 3-methoxy-1-propanol, whereas catalysis by dibutyltin dilaurate enhanced the reaction rates of 3-methoxy-1-propanol more than those of 2-methoxy-1-propanol and of 1-methoxy-2-propanol. Dibutyltin dilaurate has been found to impart a high ratio of Kprimary/Ksecondary, where the primary alcohol was 3-methoxy-1-propanol and the secondary alcohol was 1-methoxy-2-propanol. Determinations of mixtures in toluene solutions containing up to 75%, of 3-methoxy-1-propanol were made with good accuracy.
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  • 54
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    Journal of Applied Polymer Science 9 (1965), S. 1807-1822 
    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: Particle diameters were measured in electron photomicrographs of polyethylene latexes prepared with a potassium soap, a polyethyoxylated p-alkyl phenol, or a sodium alkyl sulfate. The volume-surface average diameters calculated from these values compare well with those obtained independently by soap adsorption. Plots of the diameters on log probability paper indicate that the diameters follow a log-normal distribution. The width of the distributions is given, and its effect on the difference between the number-average and volume-surface average diameters is discussed. A study of the effect of the recipe shows that the diameter of the average particle produced in the emulsion polymerization of ethylene decreases as the amount of emulsifier is increased, but the addition of tert-butyl alcohol increases particle diameter. Particle diameter is not affected by the initiator within the concentration range normally used. During the course of polymerization, the number of particles slowly increases in the presence of tert-butyl alcohol, but in its absence the number of particles decreases. In the absence of tert-butyl alcohol, the number of particles increases as the 1.1 power of the emulsifier concentration.
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  • 55
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    Journal of Applied Polymer Science 9 (1965), S. 1853-1862 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A series of low-pressure Ziegler polyethylene samples has been fractionated by the sand column technique. The molecular weight distributions have been determined by the Schulz-Dinglinger approximation. The number-average, weight-average, and z-average molecular weights have been calculated from the fractionation data for each sample by the method of summation. Melt indexes and melt flow ratios have been determined by standard techniques. The melt index is found to be related to the reciprocal of the fifth power of the weight-average molecular weight, and the melt flow ratio is proportional to the z-average molecular weight.
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  • 56
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    Journal of Applied Polymer Science 11 (1967), S. 357-368 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Previous studies by Black and Blomquist on the degradative failure of polymer-metal adhesive bonds have shown that composite failure depends largely on the type of metal substrate employed. In the work reported herein, metal powders of high surface area have been employed to maximize the metal-polymer interface. The composite systems studied consisted for aluminum and iron with polycondensates of bisphenol A-diglycidyl ether, phenol-formaldehyde and poly-2,2′-(m-phenylene)-5,5′-bibenimidazole. The composites were prepared in the absence of air and thermally degraded in a time-of-flight mass spectrometer while the degradation products were continuously monitored from mass 1 to 200. In the polymer and polymer-metal systems investigated, iron accelerated the decomposition of all polymers studied. This was determined by plotting m/e against degradation temperature for the more common mass peaks such as hydrogen and carbon monoxide for the carbon-hydrogen-oxygen-containing polymer and hydrogen cyanide and ammonia for the carbon-hydrogen-nitrogen-containing polymer. This technique offers promise in determining the nature of the interface as well as the effect of the interface on polymer degradation.
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  • 57
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    Notes: A study was made of the influence of selected chain modifiers on both the molecular weight of grafted polyacrylonitrile and the grafting frequency of the starch-polyacrylo-nitrile graft copolymer. Gelatinized wheat starch was used with ceric ammonium nitrate as the initiator. The organic chain modifiers investigated were ethyl mercaptan, 1-dodecanethiol, methyl ethyl ketone, acetaldehyde, and chloroform. Sodium chromate, cupric bromide, cupric nitrate, cupric acetate, and cupric chloride were also tested as chain modifiers. In the presence of cupric chloride, there was a tenfold reduction in the molecular weight of grafted polyacrylonitrile; however, fewer chains were grafted to the starch backbone than were observed without cupric chloride.
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    Journal of Applied Polymer Science 11 (1967), S. 475-478 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 59
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    Journal of Applied Polymer Science 11 (1967), S. 499-514 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The supermolecular structure of mixtures of crystalline polymers (low pressure and high pressure polyethylene, isotactic polypropylene) with an amorphous polymer (atactic polypropylene) from the point of view of the influence of the amorphous component on the morphology of the crystalline component has been investigated. The criterion of changes in the morphological state of larger supermolecular formations was the microscopic image of the samples obtained with an optical microscope, both between crossed nicols and in phase contrast. It has been established that the formation of typical spherulites depends on the amount of admixture of the amorphous polymer and also on the treatment of the samples. Upon crystallization in presence of a small amount of solvent (p-xylene), formation of typical spherulites of the crystalline component of the mixture can be observed while the same mixture in case of evaporation of the solvent presents a granulated refractive structure without typical spherulites, regardless of the rate of cooling. The probable role of the solvent is to facilitate mutual segregation of the microphases of both polymers in consequence of decrease in viscosity of the mixture. It has been further shown that even after briefly heating the mixture to a temperature of 220°C., before crystallization, spherulites do not form; on the contrary, spherulites originally present disappear and a structure consisting of smaller refractive formations of crystalline polymer is obtained. The formation of this structure, emerging after destruction of spherulites, might be attributed to an increase of interpenetration of both polymers and to an increase of the contact surfaces between components of the mixture.
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  • 60
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    Notes: An experimental assembly incorporating a capacitance-type, differential pressure transducer, which provides resolutions of 3 × 10-4 torr at pressures extending to 30 torr, has been employed to monitor the effect of hydrogen environmental pressure on the hydrogen yield from x-irradiated polyethylenes. Contrary to the observations of previous investigators, the hydrogen yield is found to be independent of hydrogen environmental pressures extending over the critical range up to at least 30 torr. It is demonstrated that neglecting the temperature and density gradients inherent in closed-volume irradiation assemblies employing cryogenic traps to separate liberated gases into condensable and noncondensable fractions may lead to erroneous conclusions with respect to gas yields arising from the irradiation of materials. A homogeneous, variable-plate separation ion chamber consisting of a polyethylene body and utilizing flowing ethylene as the cavity gas was employed to obtain total volatile G values of 3.6 ± 0.4, 3.8 ± 0.4, and 4.0 ± 0.4 molecules/100 e.v., for Marlex 6002, Dow Ziegler (Q 917.5), and DuPont A-1410 polyethylenes, respectively. A hydrogen contribution of approximately 98 mole-% was obtained with this experimental method.
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    Journal of Applied Polymer Science 11 (1967), S. 601-602 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 62
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    Journal of Applied Polymer Science 11 (1967), S. 629-638 
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    Notes: Castor oil has been used to prepare millable elastomers by using 2,4-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate, respectively. These elastomers are vulcanized with sulfur and 4,4′-diphenylmethane diisocyanate separately by using the standard methods of rubber technology, and the properties of these vulcanizates are reported.
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    Journal of Applied Polymer Science 11 (1967), S. 673-685 
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    Notes: A model nucleating agent for polypropylene crystallization is described. A series of compounds consisting mainly of organocarboxylic acid salts is evaluated as heterogeneous nucleating agent for polypropylene crystallization by measuring their effect upon the polymer supercooling. Sodium benzoate and basic aluminium dibenzoate were among the best nucleating agents found. The nucleating abilities of the various compounds are discussed in terms of their structural features.
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    Journal of Applied Polymer Science 11 (1967), S. 705-718 
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    Notes: We have shown by two separate measurements that polypropylene when melted after irradiation undergoes crosslinking from the inception of irradiation. The first proof was an immediate increase in the solution viscosity of a narrow molecular weight fraction of polypropylene. The second proof was the marked change in melt-flow properties on irradiation of a broad molecular weight distribution polypropylene. These findings tend to support one of the two currently held views on the action of radiation on polypropylene. In addition we have confirmed previous reports that melting after irradiation contributes to the overall crosslinking reaction.
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    Journal of Applied Polymer Science 11 (1967), S. 751-751 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Applied Polymer Science 11 (1967), S. 811-815 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The preparation of polyisocyanurates by the polytrimerization of isocyanate prepolymers in the presence of organometallic catalysts leads to an increase in adhesive strength at 400°F. for bonding aluminum-to-aluminum. The trimerization efficiency of several other catalysts is briefly described.
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    Journal of Applied Polymer Science 9 (1965), S. 1913-1928 
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    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The action of acetyl chloride on the fine structure of regenerated cellulose (fiber and film) has been studied by infrared and x-ray techniques. The two techniques reveal different aspects of the fine structure and are therefore complementary. The changes found on acetylation appear to show that the molecular network theory is inadequate to describe the fine structure of the samples of regenerated cellulose studied. The observed effects can be explained more satisfactorily in terms of a structure in which highly oriented crystallites are interspersed with regions that are highly oriented but not as well ordered, resulting in a variation in density across the cross section.
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    Journal of Applied Polymer Science 9 (1965), S. 2633-2633 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Applied Polymer Science 9 (1965), S. 2639-2639 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Applied Polymer Science 9 (1965), S. 1955-1971 
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    Notes: The thermal degradation in vacuum of polymers containing aromatic or heterocyclic rings linked by various groups has been studied by a weight loss method. The most stable of the polymers examined were those with —CO—, mixed —SO2— and —O—, or—SO2— linkages. The stability of these were superior to or comparable with poly-p-phenylene and poly-m-phenylene. The particular combinations of aromatic nuclei and linking groups used did not result in tractability as most of the polymers were insoluble and infusible, even though of low molecular weight. Substitution in the aromatic nuclei could improve tractability, though at the expense of thermal stability.
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    Journal of Applied Polymer Science 9 (1965), S. 1973-1980 
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    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: In order to obtain information about the particle network existing in gelled suspensions of cellulose microcrystals, the elasticity modulus was determined of series of dilutions of these gels. It was found that over a tenfold concentration range, the modulus varies as the 3.4 power of the concentration. A gel point could not be determined. A tentative model for this behavior is proposed, in which strong forces cause extensive linear aggregation, and weaker forces cause crosslinking of the linear aggregates. It is pointed out that this model is not unreasonable in the light of earlier experimental work on these gels. The results of similar experiments on gels of attrited level-off DP cellulose are also reported.
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    Journal of Applied Polymer Science 9 (1965), S. 2285-2296 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effects of the different fillers i.e., china clay, light magnesium carbonate, Pliolite S6E, and ebonite dust, on the exothermic hard rubber reaction has been studied with the help of differential thermal analysis. The data for heat evolution show some unexpected features in that china clay, a more or less inert filler, lowers heat evolution. The behavior of magnesium carbonate also can not be fully explained. Attempts have been made to explain the data for Pliolite S6E and ebonite dust on the basis of their composition and effects of the individual components on heat of reaction. The differences in initiation temperature and slope values have been explained.
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    Journal of Applied Polymer Science 9 (1965), S. 2319-2320 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Journal of Applied Polymer Science 9 (1965), S. 2297-2310 
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    Notes: The main objective of this work has been to develop some rational hypothesis for the toughness of rubber-modified glassy polymers as defined by the energy to rupture in a tensile measurement. It is shown that the rigid phase yields and that the toughness is a result of the large energy absorption involved in the cold drawing of the matrix. The rubber phase acts principally to induce a yielding in the matrix. A triaxial stress field in the environment of the dispersed particles results in local increases in free volume which aid in the initiation of cold drawing and provides the rubber with sufficient breaking stress to prevent premature crack propagation.
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    Journal of Applied Polymer Science 9 (1965), S. 2311-2318 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effects of crosslinking on cotton fabric are changed when the cotton has been chemically modified before crosslinking with an inert substituent, such as the methyl group. The main action of the inert substituent is to preserve swelling ability by hindering fiber deswelling after methylation and during crosslinking. At the levels of modification used, the crosslinking reaction appears to proceed normally, with no effects from reduction in the number of reactive cellulosic hydroxyl groups.
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    Journal of Applied Polymer Science 9 (1965), S. 2321-2336 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A condensation reaction between 5-amino-8-hydroxyquinoline and terephthalaldehyde yielded a bis-bifunctional Schiff base ligand, 5,′5-[p-phenylene-bis(methylidynenitrilo)] di-8-quinolinol, which was used to produce coordination polymers containing Mn(II), Co(II), Ni(II), Cu(II), or Zn(II) in the form of insoluble powders. The thermal stabilities of these polymers were evaluated in vacuum over the temperature range of 25-700°C. by using a newly constructed thermobalance having improved sensitivity. The results relate the decomposition of the polymers to the metal in the backbone as well as to the organic ligand to which the metal is coordinated. Some discussion is devoted to the possible modes of decomposition of these polymers.
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    Journal of Applied Polymer Science 11 (1967), S. 1283-1288 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Dry mixtures of starch with various bases were roasted in air. The effects of roasting were determined by a viscosity method. The results suggest that roasting at alkaline pH's produces covalent crosslinks. The author speculates that the crosslinks result from a combination of autoxidation and aldolization.
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    Journal of Applied Polymer Science 11 (1967), S. 1333-1343 
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    Notes: Five examples are discussed showing how gel permeation chromatography was applied to studies of polymer systems. The calculation of molecular weights from the curves was not pertinent to the studies. The only requirement was that the seperation be a size separation and the results be reproducible.
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    Journal of Applied Polymer Science 11 (1967), S. 1387-1407 
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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 heterogeneous cellulose reaction was studied by reacting cotton fiber in pyridine medium with propionyl chloride at different initial molar concentrations and at different temperatures. It has been observed that the kinetics of reaction does not follow Sakurada's diffusion equation closely, and the deviation is more noticeable at lower initial concentrations of the reagent and at lower temperatures. A non-uniform reaction rate is also evident from the time-substitution curve. The rate of substitution changes twice during the reaction, the latter change being associated with the loss of cellulose I crystal structure. In an attempt to treat the data according to simple chemical kinetics, the order has been found to decrease continuously from the beginning, suggesting thereby an autocatalytic type of behavior. However, at the finàl stages of the reaction, when the cellulose I structure was completely lost, the reaction behaved as a pseudo first-order type. The x-ray diffractograms of the reacted samples indicate that cellulose I crystallinity decreases from the beginning of the reaction and that a new crystalline lattice develops gradually. The formation of this new crystal lattice is hindered in the cellulose crystalline region due to the lack of freedom of the chains. The diffusion equation has been modified by substituting a crystallinity index for the rate of diffusion of solvent in a solvent-gel system and thus extending Sakurada's equation. A new mechanism has been proposed considering the simultaneous reactions in the amorphous and crystalline regions. This mechanism can explain the deviation of Sakurada's equation. The kinetics expressions are derived, based on the proposed mechanism. The kinetics of decrystallization of cellulose I is also presented. A satisfactory theoretical explanation is given for the fact that the fall of reaction rate occurs at the conclusion of decrystallization of the cellulose I structure.
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  • 80
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    Journal of Applied Polymer Science 11 (1967), S. 1439-1448 
    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: It is shown that the glass temperature (Tg) for homopolymers of the type —CH2—CXY—can be expressed by a simple additive equation involving two terms: (1) a parameter E which is directly related to the molar cohesion energy and (2) a parameter Es* which is a measure of restricted rotation about valence bonds. Es*, at least for a large number of polymers, is related to the Mark-Houwink Kθ value (as measured in θ solvents at Tθ) via anti-log Es* ∝ 1/Kθ2/3. It is also shown that for homologous series [e.g., poly(n-alkyl methacrylates)], there is a constant relationship between E and antilog Es*. The Tg values for copolymers may be estimated by a simple weighted (via mole fraction) summation of the E and Es* values of the components. When used in this form, a linear variation between Tg and composition is assumed, which may not be strictly correct but still yields useful approximations.
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  • 81
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    Journal of Applied Polymer Science 11 (1967), S. 1483-1494 
    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: Lattice spacings perpendicular to the molecular chain axes and crystallite orientation of dried and moist (boiled in water) bulk nylon 6 were determined by x-ray diffraction under tension of 30-300 kg./cm.2. The deformation of the specimen was also measured. The lattice spacings are changed reversibly by the presence of water in nylon 6, but the elastic moduli of the lattice are not affected. The lattice elastic modulus in the direction of the hydrogen bonds is approximately double its value in the direction normal to the hydrogen bonds. The elastic modulus of the dried nylon 6 approaches the value of the lattice elastic modulus in the direction normal to the molecular axes, while the modulus of the moist nylon 6 is several times lower. From these facts, and especially from the relations between the lattice deformation, crystallite orientation, and specimen deformation, the principal differences in the deformation mechanism of dried and moist nylon 6 were deduced. The results obtained have also made possible some general conclusions about the crystalline structure of nylon 6 and the deformation mechanism of linear polymers.
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  • 82
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    Journal of Applied Polymer Science 11 (1967), S. 1529-1538 
    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 methyl methacrylate and acrylamide onto ovalbumin was carried out with redox system with ceric ion. Initiation of grafting occurred very rapidly, and the number of grafting sites reached a maximum after about 2 min. regardless of initial ceric ion concentration. The grafted polymer chains were separated by selective hydrolysis of the protein backbone with hydrochloric acid or protease in order to characterize the graft copolymers. The grafted polyacrylamide separated by the proteolytic digestion contained a carbohydrate residue at the end of the polymer molecule. The problem of grafting sites on ovalbumin is discussed.
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  • 83
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    Journal of Applied Polymer Science 11 (1967), S. 1553-1562 
    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 process for adhering polyethylene to aluminum was developed which involves treating the aluminium substrate successively with chromic acid and then a selected organic acid. Certain organic acids utilized in this process appeared to produce a synergistic effect on the adhesion. This process, which required no modification or treatment of the polymer, resulted in peel strengths forty times greater than that obtained on untreated aluminum. Tensile shear values for the polyethylene-aluminum bond were greater than 2800 psi. The materials used for treating the metal in this system produced a maximum in the obtainable peel strength. Furthermore, minor changes in the etching acids resulted in drastic changes in the adhesion values.
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  • 84
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    Journal of Applied Polymer Science 11 (1967), S. 1613-1615 
    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 relatively simple and inexpensive automatic apparatus for chemical relaxation giving good accuracy has been developed for measurement of chemical relaxation in the gaseous phase in high polymers. The apparatus is based on a previously described balance-type stress relaxation apparatus intended for automatic operation.
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  • 85
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    Journal of Applied Polymer Science 11 (1967), S. 1581-1591 
    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 monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to Tg for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.
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  • 86
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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 effect of cooling, nucleation, and spherulitic growth rates on the properties of polypropylene is discussed briefly. A differential thermal analysis technique is described for evaluating the relative extent of heterogeneous nucleation that occurs in a particular polypropylene composition. The method is based upon a nucleating agent's ability to reduce the relatively large amount of supercooling that occurs upon crystallization of polypropylene. Compounds are shown to vary widely in their effectiveness as heterogeneous nucleating agents in polypropylene. The relationships between the degree of supercooling of a particular polypropylene composition and its relative clarity, tensile properties, density, and morphology are shown.
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  • 87
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    Journal of Applied Polymer Science 9 (1965), S. 2121-2130 
    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: It was found that chloronitroso compounds with a free non-conjugated nitroso group show a considerable sensitizing activity in respect to the process of photochemical degradation of dissolved cis-1,4-polyisoprene, which is induced by visible radiation (4000-7000 A.). The effect of 10 chloronitroso sensitizing compounds were investigated. The highest sensitizing activity was found with compounds 2,2-chloronitrosopropane and 1,1-chloronitrosocyclohexane. The maximum wavelength, of which the decrease of relative viscosity of solutions was the highest, was determined for 2,2-chloronitrosopropane. The highest sensitizing activity of chloronitroso compounds was found for wavelengths corresponding to the absorption maximum of the sensitizer added. The theory of the sensitizing activity of chloronitroso compounds is proposed.
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  • 88
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    Journal of Applied Polymer Science 9 (1965), S. 2167-2176 
    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 diffusion constants of an acidic dye (Xylene Fast Blue P) into nylon 6 monofilaments of various draw ratios have been measured at several temperatures by measuring the distance of dye penetration into the cross-sections of the sample. The results are as follows. The diffusion coefficient of dye increases, reaches a maximum at a draw ratio near 1.6, and then decreases as the draw ratio increases. The activation energy of dye diffusion obtained from the temperature dependence of dye diffusion coefficient remains nearly constant in the initial and middle stages of drawing and increases above a draw ratio of about 3, as the draw ratio increases. The change in the polymer structure during drawing is discussed on the basis of these results.
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  • 89
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    Journal of Applied Polymer Science 9 (1965), S. 2855-2877 
    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: Nylon 66 and nylon 6 yarns were exposed in air, nitrogen, and vacuum to temperatures form 136 to 215°C. for periods from 5 min. to 17.5 hr. The moisture absorption of both fibers is reduced by the exposure independently of the presence of oxygen or of antioxidant. This is ascribed to secondary crystallization. Simultaneously, the electrical resistivity is increased. The breaking strength is reduced by exposure in the presence of oxygen unless the polymer contains antioxidant. The extent of oxidative cleavage was measured by the viscosity-average molecular weight M̄v of nylon 66. Simultaneously, a reduction of the amine endgroup content was observed. It occurs only in the presence of oxygen and approaches a limit indicating that some amine groups are not subject to elimination. If oxygen is absent or the polymer protected by antioxidant, the M̄v increases. Sorption of hydrochloric acid is reduced by the exposure. Only 80% of the amine groups in the unexposed and 55% in the exposed nylon participate in acid binding at pH 2.5. The rate constants of cleavage as manifested by M̄v and of the process leading to disappearance of amine groups were determined for nylon 66. The activation energies were calculated 40 and 36 Kcal./mole, respectively.
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  • 90
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    Journal of Applied Polymer Science 9 (1965), S. 2927-2927 
    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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  • 91
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    Journal of Applied Polymer Science 9 (1965), S. 2927-2927 
    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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  • 92
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    Journal of Applied Polymer Science 9 (1965), S. 2929-2938 
    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 preparing a latex with a particle size larger than can be obtained by direct emulsion polymerization. It consists in growing latex particles to larger size by feeding more monomer and adjusting the emulsifier concentration in a manner which prevents both coagulation and the formation of new micelles.
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  • 93
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    Journal of Applied Polymer Science 9 (1965), S. 2939-2954 
    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 anionic polymerization of caprolactam (with sodium hydride and acetyl caprolactam as catalysts) carried out in glass ampules is reported. The effect of the catalyst concentration, polymerization temperature, and other variables was studied. Polymerization of caprolactam at temperatures around 120°C. in a paraffin suspension, in which the paraffin was introduced into a syrupy prepolymer is also reported. The influence of a few variables on conversion, molecular weight, particle size distribution, is discussed. Both viscosity and conversion are always lower in suspension than in bulk polymerization. Polymer granules of a wide range of dimensions which generally contain some residual monomer (unlike the bulk polymerization) are obtained in suspension polymerization. The above results are discussed and some interpretations are suggested.
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  • 94
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    Journal of Applied Polymer Science 9 (1965), S. 2955-2964 
    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: Attempts to prepare block or graft copolymers of isobutylene rubbers by radiation in the presence of methyl methacrylate gave low yields of copolymer with only 20% of the rubber entering into the copolymer. The remainder of the rubber is degraded during the process. A single experiment describes the graft copolymerization of methyl methacrylate with ethylene-propylene rubber in which 45% of the rubber is copolymerized.
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  • 95
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    Journal of Applied Polymer Science 9 (1965), S. 3605-3616 
    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: Cast amorphous one mil films of poly(ethylene terephthalate)were allowed to crystallize isothermally in silicone oil over the temperature range 25-240°C. The crystallization paths were followed by recording the percent of transmission of 4000 A. light through the films as a function of time at specific temperatures. At temperatures between 70 and 90°C. the transmission increased to a value higher than the initial transmission and did not decrease with time. From about 95 to 125°C. the curves showed a similar increase, followed by a decrease to a minimum and then an increase to a new maximum before leveling off. The shapes of these curves were interpreted in terms of the sizes of the growing spherulites. The first detectable signs of crystallization were observed at 96.5°C., as evidenced by density and densitometer measurements. It is shown that the polymer passed through a temperature range beginning at the glass transition point (66°C.) and extending to about 95°C., where molecular and chain rearrangements occurred without crystallization. Half lives and rate constants were found to increase exponentially over the range 96.5-119.5°C. Above approximately 125°C., the crystallization process took place at such a rapid rate that accurate data were impossible to obtain. Activation energies were calculated from the rate constants and from an estimation of induction times from the light transmission-time curves. These values were found to be 37 and 30 kcal./mole, respectively. The density-time data were also fitted to the Avrami relationship. Evaluation of the constants indicated that the initial crystallization growth was lineal.
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  • 96
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    Journal of Applied Polymer Science 9 (1965), S. 3625-3633 
    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 new acrylate and methacrylate ester monomers and polymers which contain three different m-dioxane rings are described. All homopolymers have high secondorder transition temperatures and softening points and one methacrylate polymer has the highest value reported for an acrylic ester polymer. The m-dioxane ring provides a site for crosslinking homopolymers and copolymers by acid and/or peroxide. The order of reactivity of the polymers in crosslinking by peroxide and acid is different, suggesting that ionic and free-radical mechanisms are involved. The order of reactivity is discussed in terms of the structure of the side chain dioxane rings. Oxygen plays a role in the peroxide crosslinking reaction. One of the m-dioxane rings in monomer or polymer form is readily opened by water to form hydroxyl-containing materials.
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  • 97
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    Journal of Applied Polymer Science 9 (1965), S. 3635-3648 
    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: Epoxy compounds such as allyl glycidyl ether, phenyl glycidyl ether, and Epicote 812, which are not polymerizable by irradiation, were irradiated by γ-rays to a total dose of 1 × 107-2 × 108r, and decomposition of epoxy radicals was examined. The result showed that epoxy radicals are more or less radiation-resistant and for the greater part remain unchanged. Methacryl glycidyl ester, which is polymerizable by irradiation, was radiation-grafted to polyethylene and to polytetrafluoroethylene by simultaneous irradiation with γ-rays, and the degree of grafting was checked. Two sheets of radiation-graft polyethylene or polytetrafluoroethylene were bonded with epoxy resin adhesives containing polyamide hardener, and bond strength was examined. This showed that the bond strength of grafted polymer is larger than that of the nongrafted one.
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  • 98
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    Journal of Applied Polymer Science 9 (1965), S. 3661-3680 
    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: Monomeric acrylic acid when placed between two polymeric films may be polymerized almost explosively at a dose of 0.3 Mrad with electrons. The resultant exotherm leads to bonding of the two films and the preparation of an interlaminar layer of polyacrylic acid. Changes in oxygen permeability are found for the resultant sandwich. The exotherm and the resultant bonding is dependent on the dose rate, dose, and the volume of acrylic acid used for the interlaminar layer. The results qualitatively follow the mechanism for explosive polymerization discussed by Semenov and more recently by Chachaty, Magat, and Ter Minassian.
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  • 99
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    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 viscoelastic properties of films of unsaturated fatty acid-modified alkyd resins prepared by different synthetic procedures are examined. The films prepared by the fatty acid method have a higher glass transition temperature and greater degree of crosslinking than those prepared by the monoglyceride method. It is suggested the molecular weight distribution of prepolymer prepared by the monoglyceride method would be broader than that prepared by the fatty acid method, and this was verified by the results of [η]/Mn and fractionation of prepolymers. The differences in viscoelastic properties of films is explainable on the basis of the molecular weight distribution and the distribution of crosslinking functional groups of prepolymers.
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  • 100
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    Journal of Applied Polymer Science 9 (1965), S. 3681-3700 
    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: Additional studies have been conducted on the radiation-induced, solid-state polymerization of trioxane. The out-of-source polymerization rate has been investigated as a function of radiation dose and of temperature and time of polymerization. The empirical relationship of log time ∝ Y (where Y is the polymerization percentage) was found to be satisfactory over wide ranges of conversion, of dose, and of polymerization time. At a given dose, the yield was directly proportional to the RSV1.33 (where RSV is the reduced specific viscosity). Either increasing the dose or decreasing the particle size gave lower RSV values at the same conversions.
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