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  • Polymer and Materials Science  (3,704)
  • 1980-1984
  • 1965-1969  (3,261)
  • 1950-1954  (443)
  • 1969  (1,791)
  • 1966  (1,470)
  • 1953  (443)
Collection
Publisher
Years
  • 1980-1984
  • 1965-1969  (3,261)
  • 1950-1954  (443)
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 2
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 3
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 4
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 5
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 6
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 7
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 8
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 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: 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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  • 10
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 11
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 12
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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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  • 13
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    New York, NY [u.a.] : Wiley-Blackwell
    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
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 14
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    New York, NY [u.a.] : Wiley-Blackwell
    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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  • 15
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 10 (1966), S. 551-574 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polymerization of vinylcarbazole in aqueous dispersion by azobisisobutyronitrile can yield-depending on the protective colloid used-polyvinylcarbazole beads or granules. These require impregnation by a polymer solvent and preferably also by azobisisobutyronitrile before they can be molded to panels or simple shapes.
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  • 16
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 10 (1966), S. 653-661 
    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: Data are presented relating the time change of the coefficient of friction of cast polypropylene films to changes in film density and concentration of surface lubricant. It is shown that during aging the density of polypropylene increases, thus causing a decrease in the friction coefficient. It is also shown that although the lubricant added to the polymer will diffuse to the surface of copolymer films, no diffusion occurred in polypropylene films.
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  • 17
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    Journal of Applied Polymer Science 10 (1966), S. 1214-1214 
    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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  • 18
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    Journal of Applied Polymer Science 10 (1966), S. 1247-1259 
    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: The study of factors influencing the adhesion properties of polyurethane coatings to aluminum has been continued. The data indicate that the addition of additives to polyurethanes can affect their peel strengths. The addition of epoxy resins, chlorinated paraffins, or sulfonamide-formaldehyde resins results in increased peel strengths; the use of a mixture of fatty acids resulted in reduced values. The isocyanate structure can also play an important role; those producing more flexible films (such as m-xylylene di-isocyanate) result in higher peel strength values. Other factors found to be of importance included the concentration of aromatic and aliphatic groups, the type of solvent used in casting the films, the crystallinity of the polyether glycols and the presence or absence of certain substituents, such as fluorine, in the polyurethane chain. Tracer studies have indicated that the mechanism of adhesion failure involves the breaking of the polymer-polymer as well as polymer-substrate bonds.
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  • 19
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    Journal of Applied Polymer Science 10 (1966), S. 1315-1322 
    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 effects of a filler in an elastomer can be described by means of a theory based on a simple model in which the filler particles are assumed to be of uniform size, of cubic shape, and dispersed in such a manner as to occupy the points of a cubic space lattice. For the case of shear deformation, simple relations can be derived for the increase in the storage modulus G' and the loss modulus, G″ of the bulk material with an increase in filler content. Furthermore, the theory predicts the temperature shift of two points which can be easily determined experimentally: the inflection point of G' and the maximum of G″.
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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: Young's modulus and the mechanical damping factor have been determined between -180 and +280°C. (at a frequency of several kilocycles), in samples of isotactic polypropylene, isotactic polystyrene, and trans-1,4-polybutadiene, subjected to pile irradiation (γ-rays and neutrons) at γ-doses from 90 to 4000 Mrad. In isotactic polypropylene no important structural changes are produced by the irradiation, except for a partial destruction of crystallinity. The samples receiving high radiation doses exhibit a low temperature loss region, which is attributed to the formation of a certain number of branches. Isotactic polystyrene shows very slight modifications of the dynamic mechanical properties at room temperature. At low temperature an increase of intensity of the δ relaxation phenomenon (probably due to oscillations of phenyl rings) with increasing radiation dose is observed. Important structural modifications produced by the radiation, destruction of crystallinity accompanied by crosslinking, which transform the material into a crosslinked rubber, are observed in trans-1,4-polybutadiene. Unlike conventional (sulfur) vulcanization, crosslinking by radiation does not cause a marked shift of the glass transition point. A secondary low-temperature relaxation effect, not existing in the unirradiated material, appears in the mechanical loss curves of the irradiated samples; it is attributed to the formation of —CH2—sequences in the main chains through saturation of C=C bonds. The mechanical spectrum of irradiated polybutadiene is very similar to those shown by crosslinked ethylene-butadiene copolymers.
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  • 21
    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: New methods for the treatment of cotton with acrylamide have been studied which permit the preparation of modified fabrics with relatively high degrees of carboxyethyl substitution. Wet treatment with acrylamide and sodium hydroxide can be used to produce cottons bearing both carboxyethyl and carbamoylethyl ether substituents. Adjustment of reaction conditions controls the amount and ratio of these substituents. The effects of varying the concentrations of the reactants, the time and the temperature of reaction, and the solvent media employed have been determined. Some elucidation of the chemical mechanisms is provided. Previous work has shown that dry heat treatments of cotton impregnated with acrylamide and alkali can be used to produce high carbamoylethyl substitutions with little or no carboxyethyl substitution. The present work provides an extension of the cotton-acrylamide treatment whereby fabrics can be produced with only carboxyethyl or carbamoylethyl groups, or with mixtures of the two.
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  • 22
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    Journal of Applied Polymer Science 10 (1966), S. 767-771 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: It is shown that some results of recent publications (of Longworth and Piesky and of Bartoš) can be treated as particular consequences of the principle of universality of temperature-independent viscosity characteristics of polymer melts, earlier found by these authors. This concerns the method of determination of molecular weight by means of melt index measuring and supposition that the definite value of apparent viscosity to initial Newtonian viscosity ratio can be considered to be a criterion of elastic turbulent flow emerging.
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  • 23
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    Journal of Applied Polymer Science 10 (1966), S. 813-823 
    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: Various expressions are presented for the estimation of kinetic parameters during pyrolysis from DTA traces. These expressions are applied to polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, isotactic poly(propylene oxide), and poly(methyl methacrylate). The results obtained are compared with reported values, and advantages and disadvantages of the various methods are given.
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  • 24
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    Journal of Applied Polymer Science 10 (1966), S. 865-885 
    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 monomolecular film behavior of polyvinyl acetate (PVAc), polyethyl acrylate (PEA) and mixtures of these ranging in concentration ratio of PEA to PVAc from 0.008 to 11.301 has been studied using a Langmuir-type filmbalance over an aqueous 0.01N HCl substrate. Hysteresis was observed in the compression-expansion cycle for PVAc. A discussion of polymer-polymer interaction in a mixed monomolecular film at an interface is presented. The extent of this interaction for films comprising PVAc and PEA has been determined in terms of deviations of the film area from the ideal behavior. The data on the film areas of PVAc and PEA are discussed in terms of the molecular orientation of these polymers on the surface. A simple equilibrium thermodynamic treatment is applied to the data on mixed monolayer films. The implications resulting from this study are discussed.
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  • 25
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    Journal of Applied Polymer Science 10 (1966), S. 925-928 
    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: Viscosity parameters were obtained for maize maylose (molecular weight of 107,000) in 1N KOH at 25, 30, 35, and 40°C. Intrinsic viscosity continuously decreased and Huggins' constant k' continuously increased with increasing temperature. The temperature dependence of intrinsic viscosity, d[η]/dT, was -2.12 × 10-2/°C.
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  • 26
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    Journal of Applied Polymer Science 10 (1966), S. 969-979 
    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 salt rejection properties of cellophanes are substantially increased, and permeation rates decreased, by pretreatment with certain metal ions or presence of these ions at low concentration in feed solutions. In a typical case, a cellophane which initially rejected about 20% of salt from a 0.05M NaCl solution rejected over 70% in Presence of 10-3M ThCl4. Permeation rates were decreased, usually be a factior of 2 or 3. Additives found to have a marked effect were Fe(III), Th(IV), U(VI), Cu(II), and hydrolyzed pb(II). Mg(II), Ba(II), La(III), and unhdrolyzed Pb(II) had little effect. The mechanism by which the additives affect the cellophane is not clear.
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  • 27
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    Journal of Applied Polymer Science 10 (1966), S. 993-1009 
    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: Alkyds prepared from castor and hydrogenated castor oils have been prepared direct from the oil and by first subjecting the oil to a glycerolysis reaction. The molecular weight distributions of the alkyds have been measured in solvent systems designed to separate predominantly on polarity and molecular weight. The properties of the alkyds in stoving enamels have been evaluated. The results are discussed in relation to existing theories relating processing conditions to molecular weight distribution in alkyd resins. Previous suggestions regarding the reactivity of the hydroxyl groups in the oil molecules are not consistent with the results obtained in this study.
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  • 28
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    Journal of Applied Polymer Science 10 (1966), S. 1099-1110 
    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: Eyring's theory of viscous flow has been applied to some mechanical properties of rubber-modified polystyrenes. Yield strength as a function of orientation, temperature, of transition from ductile to strain have been shown to be consistent with the theory. The temperature of transition from ductile to brittle fracture as a function of orientation has also been measured and found to be consistent with theoretical predictions.
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  • 29
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    Journal of Applied Polymer Science 10 (1966), S. 1153-1170 
    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 addition reaction between melamine and formaldehyde has been kinetically separated from the subsequent condensation stage by suitable choice of concentration and temperature conditions. The reaction, which is reversible, has been monitored by estimation of the free formaldehyde content of the system. It has been investigated over the range of mean degree of methylolation 1 〈 R′ 〈 3.7 of the melamine nuclei, the temperature range 25-55°C., and the pH range 5.7-10.2. The rate data thus obtained have been treated according to the random reversible addition scheme for which reasonable, first approximation, agreement was obtained. Average kinetic and thermodynamic constants have been calculated and are discussed in terms of the present model. The factors which are likely to cause deviations from randomness are described. The addition of formaldehyde to melamine proceeds by superposition of an OH--catalyzed step with a minor solvent-catalyzed or uncatalyzed one.
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    Journal of Applied Polymer Science 10 (1966), S. 1213-1213 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 31
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    Journal of Applied Polymer Science 10 (1966), S. 1217-1228 
    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: Wool has been modified to render it more hydrophobic by two methods. The first method involved treating the wool with benzoyl, lauroyl, stearoyl, and dodecenyl chlorides and with trifluoroacetic anhydride. Substantial degrees of reaction with the wool were achieved when the correct solvent media and reaction conditions were used. These varied with the particular reagent employed. Pyridine was particularly effective with the acid chlorides, whereas dimethyl sulfoxide was best with trifluoroacetic anhydride. Pyridine is believed to function both as a swelling agent and as an acid acceptor in these treatments. The second method of treatment was the grafting of vinyl and allyl monomers to wool by the use of high energy radiation. Both 60Co γ-rays at 0.3 Mrad/hr. and Van de Graaff γ-radiation at 3 Mrad/min. were found to be highly effective. The presence of a swelling agent in the monomer solution was found to be essential even in the case of acrylonitrile in dimethyl formamide. Water and methanol in small amounts were found to be highly efficient swelling agents. Substantial quantities of monomer could be grafted in most cases without difficulty when the correct conditions were used.
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  • 32
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    Journal of Applied Polymer Science 10 (1966), S. 1285-1294 
    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: High quality packaging films from hydroxyethyl cellulose of low degree of substitution (DS) are being produced commercially in this country and abroad. Increasing demand for this and a variety of other applications requires a rapid and simple production control method for determining hydroxyethyl substitution of cellulose. None of the known analytical methods fulfills these requirements. The present paper describes a method which is based on the relationship between the solubility and the molar hydroxyethyl substitution of hydroxyethyl cellulose. A washed and dried sample of hydroxyethyl cellulose is dissolved in 7% aqueous sodium hydroxide. Methyl alcohol, a nonsolvent, is used to precipitate a fraction of the sample. The turbidity of the equilibrium system is determined and optical density readings are related to molar substitution. The method is most useful in low DS ranges of 2-8% EtO but is susceptile to broader application through adjustment of the composition of the solvent-nonsolvent mixture. Relatively large variations in DP can be tolerated. The molar substitution level of an hydroxyethyl cellulose sample can be obtained in 40 min. by this method, making it a practical production control technique.
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  • 33
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    Journal of Applied Polymer Science 10 (1966), S. 1295-1303 
    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: Comparison of aging of a sulfur vulcanizate with a control having stable crosslinks, shows that oxygen affects reactions of the crosslink as well as of the hydrocarbon. Crosslink scission is inhibited. Results are in agreement with an earlier Suggestion that new crosslinking is enhanced by oxygen, although less than observed for natural rubber. This may be an effect of carbon black and amine antioxidants present in the vulcanizates.
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  • 34
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    Journal of Applied Polymer Science 10 (1966), S. 1343-1350 
    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 Sward rocker tester is used to obtain the Sward number for glass, mild steel, copper, poly(methyl methacrylate), polyethylene of various densities, and natural rubber. A relationship between the number and mechnical properties is investigated. It is shown that with metals and glass the number is essentially a frictional factor. With plastics and rubber it is a true hardness factor, involving dynamic Young's modulus, Poisson's ratio, and damping capacity. The aim of the investigation is to encourage the development of the Sward test as a nondestructive quality test for plastics.
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  • 35
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    Journal of Applied Polymer Science 10 (1966), S. 1409-1419 
    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: Isothermal crystallization of poly[3,3-bis(chloromethyl)oxacyclobutane] and poly-(ethylene terephthalate) from the quenched glassy state gave small lamellae approximately 1000-2000 A. in lateral dimension with a constant thickness of about 100 A. The maximum primary nuclei density for crystallization slightly above the glass transition temperature, Tg, was 1010 greater than frequently observed during spherulitic growth from the melt. Since the lamellae grow at a linear rate, the crystallization process could be described by the Avrami theory for two-dimensional growth with a constant nuclei density. By assuming that crystallization near Tg is diffusion-controlled, bulk crystallization rate data were analyzed to obtain self-diffusion coefficients whose activation energies were similar to reported values for other polymers.
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  • 36
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    Notes: As one in a series of studies relating the rheological behavior of mechanical mixtures of two polymer components to the degree of mixing, the tensile stress relaxation behavior of a graft copolymer of poly(vinyl acetate) with styrene, obtained by 60Co γ-irradiation of poly(vinyl acetate) in styrene solution and extraction of homopolymers, was investigated as a function of the fraction of styrene component and compared with that of a mechanical mixture of poly(vinyl acetate) with polystyrene, one of the typical combinations of incompatible components. The results obtained may classify the graft copolymer as a sort of mechanical mixture giving stable mixing even for incompatible components.
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  • 37
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    Journal of Applied Polymer Science 10 (1966), S. 1845-1862 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some Physical, chemical, and solution properties of polyethylene prepared by emulsion polymerization are described and compared with those of conventional high-pressure polymer. The emulsion polymers contain an unusually large amount of low molecular weight material for the solution viscosities they exhibit. It is this low molecular weight material that contributes to the characteristic low elongation of the emulsion polymer, as well as to its wide distribution of molecular weights. The effect of changes in recipe and in conditions of polymerization on these properties is discussed. It is shown that some of the emulsifier present during polymerization becomes part of the polymer chain.
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  • 38
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    Journal of Applied Polymer Science 10 (1966), S. 1929-1935 
    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 artifact observed in point projection microradiographs of polymeric fiber and filaments obtained with 8-A. x-rays is recorded and described. The phenomenon has been related to fiber-beam geometry and the high reflection efficiency of soft x-rays for these materials.
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    Journal of Applied Polymer Science 10 (1966), S. 1937-1947 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The unfolding of the α-helices of the microfibrils in α-keratin fibers such as wool proceeds in a cooperative manner. When a wool fiber is extended in water, the load-extension curve obtained indicates on the basis of relationships derived from rate process theory, that the number of α-helical residues n that unfold simultaneously is at least 50. This is probably an underestimation, as fiber diameter variability severely reduced any estimate of the value of n. Other experimental evidence is also indicated that support the existence of considerable mechanical cooperation between α-helical components.
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  • 40
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    Journal of Applied Polymer Science 13 (1969), S. 1845-1858 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Mercaptan and disulfide contents of modified cotton fabrics could be determined by application of Leach's polarographic method for wool, with minor modification.It was found that mercaptocellulose prepared by the reaction of tosyl cellulose and potassium thiolacetate followed by alkaline hydrolysis contained considerable amounts of disulfided in addition to mercaptain. Iodometric titration of mercaptocellulose gave a higher value of mercaptan than that obtained by the polarographic method. The mercaptan and disulfide contents and methylene blue uptake of the iodine-treated samples indicate that some of the mercaptan groups further undergo oxidation to acidic groups as a result of the iodine treatment.The spatial effect in the oxidation of mercapto groups in modified cotton is briefly discussed.
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  • 41
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    Notes: The catalysis of the reaction of n-butyl alcohol with isocyanates, using organometallic derivatives of lead, tin, and mercury, has been investigated. The rate of the reaction was measured by following the disappearance of the isocyanate absorption in the infrared. Phenyl, n-butyl, and cyclohexyl isocyanate were chosen to represent typical aromatic primary and secondary aliphatic isocyanates. Within the same series of catalysts, RnMOAc, the catalytic effect decreases in the order RHg 〉 R3Sn 〉 R3Pb; and in all cases R = aryl 〉 R = alkyl. The electronic effects of substituents on the aryl moiety are not pronounced. Changes in X of RnMX greatly affect the catalytic activity. The mechanism of organometallic catalysis of the alcohol-isocyanate reaction occurs via a template-type mechanism whereby the catalyst acts to complex both reactants in a catalyst phase allowing the reaction to occur with greater facility.
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  • 42
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    Journal of Applied Polymer Science 13 (1969), S. 1-7 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polymerization of N-vinylcaprolactam in toluene, dioxane, chlorobenzene, dimethylformamide, and ethylene carbonate with various peroxides, perbenzoates and azobisisobutyronitrile as initiators at 60-80°C, was studied. Under these conditions azobisisobutyronitrile and tert-butyl perbenzoate have satisfactory activity as initiators. Under these conditions N-vinylcaprolactam polymerization in homogeneous solution is first order towards the monomer and 0.5 order towards the initiators.
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  • 43
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    Journal of Applied Polymer Science 13 (1969), S. 9-15 
    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 study has been made of the photolysis and photo-oxidation of phenoxy resin. Photolysis results in the evolution of hydrogen, methane, ethane, propene, propane, toluene, and the oxides of carbon. Also observed are increased yellowing, a rapid rise in gel content, and a decrease in intrinsic viscosity and elongation. Photo-oxidation causes similar changes, but produces oxidized chain fragments, more gel, and less yellowing as well as broad absorptions in the hydroxyl and carbonyl regions of the infrared spectrum. A free-radical mechanism is proposed in which both chain scission and crosslinking occur.
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  • 44
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    Journal of Applied Polymer Science 13 (1969), S. 2069-2072 
    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: Glass transitions in certain polymer samples were detected as a step change in a DTA trace in the exothermic sense. This anomaly is explained as a manifestation of the volume relaxation shown to occur at the glass transition in internally strained samples.
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  • 45
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    Journal of Applied Polymer Science 13 (1969), S. 2057-2068 
    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 an ion radical complex is formed by the reaction of carbon black with an alkali metal (Li, Na, K) in tetrahydrofuran. The graft copolymerization of styrene with carbon black was carried out using the ion radical complexes as initiator, and free polystyrene and carbon black-polystyrene graft copolymer were obtained. The identification of the graft copolymer with carbon black was carried out by fractionation and thermal degradation. The initiation activity of the alkali metals increased in the order Li 〈 Na 〈 K. The effect of the particle size of the carbon black on the graft copolymerization was studied.
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  • 46
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    Journal of Applied Polymer Science 13 (1969), S. 29-40 
    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: From the viewpoint of continuum mechanics, and particularly the energy concept of fracture, adhesive and cohesive failures are similar. The essential difference involves the interpretation of the energy required to create new (adhesive or cohesive) surface area. A simple pressurized disk test is described for measuring the adhesive value for a bonded elastomer, and an application to a debonding problem in engineering design is given.
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  • 47
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    Journal of Applied Polymer Science 13 (1969), S. 41-54 
    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 study of the swelling of Acala 4-42 cotton in aqueous alkalis and acids has been carried out. The degree of swelling of the cotton in the reagents has been indicated by measurement of the variations in width of the cotton at its widest point. The nature of the swelling process whether interfibrillar or intrafibrillar has been deduced from microscopical and x-ray evidence. It has been shown that a similarity of shape of the swelling curves, i.e., an equal degree of swelling in the same or other reagents, does not imply the same mechanism of swelling. The results are more readily explained in terms of the crystalline-fibril theory than by the fringe-micellar theory, especially when high degrees of swelling have been achieved.
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    Journal of Applied Polymer Science 13 (1969), S. 55-67 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We have investigated the high temperature mechanical behavior of several unplasticized emulsion- and suspension-prepared whole polymers, and carried out molecular weight, molecular weight distribution, and branching characterization studies on these same materials. It is concluded that the easier workability of the emulsion product is probably due to the absence of a considerable amount of high molecular weight polymer in these as compared to suspension-prepared polymers of equal average molecular weight as reflected by intrinsic viscosity determinations of Fikentscher K values.
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  • 49
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    Journal of Applied Polymer Science 13 (1969), S. 69-80 
    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: Capillary rheometer measurements show that stearic acid can be characterized as a normal lubricant. If the content of stearic acid is increased in rigid PVC formulations, the melt viscosity will decrease. This leads to a corresponding increase of shear rate and volumetric flow rate. The influence of calcium stearate is opposite to the normal characteristic of a lubricant. Increasing amounts of calcium stearate lead to an increased melt viscosity and a decreased shear rate and volumetric flow rate. In the extrusion of rigid PVC, the apparent “lubricating” effect of calcium stearate is probably due to the increased friction with resulting heat evolution and higher mass temperature, leading to a decreased viscosity of the plastic melt. This is in agreement with the results of the extrusion experiments. Both mass temperature and power consumption decrease when stearic acid is added and increase when calcium stearate is added to the formulation.
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    Journal of Applied Polymer Science 13 (1969), S. 2193-2207 
    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 on the peel behavior of pressure-sensitive tape comprising a polyester backing and polyacrylate adhesive have shown that, in peeling from a plane glass surface, three fundamentally different modes of peeling may be distinguished, depending upon the rate of pulling. At low rates, deformation by flow of the adhesive appears to determine the peel behavior and the peel force is strongly rate dependent. At high rates, little or no viscous deformation of the adhesive occurs and the peel force is independent of rate. At intermediate pulling rates, cyclical instability of made of failure involving alternate storage and dissipation of elastic energy in the backing, results in the phenomenon of “slip-stick” peeling, in which failure is jerky and regular. Results have been obtained which show how the pulling rates at which transitions from one mode of peel to another occur, and the peel force values for a given type of failure, depend upon such factors as molecular weight of adhesive, thickness of backing film, and angle of peeling.
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  • 51
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    Journal of Applied Polymer Science 13 (1969), S. 2247-2255 
    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 reactions of trans-2,5-dimethoxy-4′-aminostilbene with poly(maleic anhydride-co-methylvinyl ether) and trans-2,5-dimethoxy-4′-isocyanatostilbene with poly(oxy-1,4-phenyleneisopropylidene:1,4-phenyleneoxy-2-hydroxytrimethylene) yield polymeric systems which undergo rapid crosslinking upon short exposure to ultraviolet light. The extent of photocrosslinking as a function of exposure time was determined by the decrease of the trans-stilbene ultraviolet absorption at 350 nm.
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  • 52
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    Notes: Diethylaminoethyl (DEAE)-cotton has been reacted with epichlorohydrin (1,2-epoxy-3-chloropropane) neat, in alcoholic solvents, and in aprotic solvents at temperatures ranging from 25 to 95°C. Fabric properties and electron micrographs of fibers removed from these chemically treated DEAE cottons have been compared with those obtained when DEAE-cottons were treated under similar conditions with other halogenated 1,2-epoxypropanes, and with 1,2-epoxy-4,4,4-trichlorobutane. For comparative purposes, epichlorohydrin was reacted with an aminized cotton containing primary amine groups, with cotton containing quarternary ammonium groups, and with DEAE-cottons in which the tertiary amine groups had been quaternized. For reaction at 95°C with net epichlorohydrin, greatest increase in conditioned wrinkle recovery was observed with DEAE-cottons. Only with DEAE-cottons were the add-ons and recovery angles imparted by epichlorohydrin affected by the anion associated with the amine groups. None of the halogenated 1,2-epoxypropanes reacted with unmodified cotton in the absence of a basic catalyst. Those that reacted with unmodified cotton in the presence of an external base catalyst did not improve conditioned recovery angles. The mono-, di-, and trichloro-1,2-epoxypropanes all increased the conditioned and wet wrinkle recovery of DEAE-cotton when reacted neat at 95°C. The type of oxirane ring opening of epoxypropanes was shown to be influenced by the degree of chlorination of the carbon alpha to the ring. Both primary amine groups and quaternary amine groups catalyzed the epichlorohydrin-cellulose reaction. Dilution of epichlorohydrin with alcohols or decreasing reaction temperature lowered add-ons and improvements in wrinkle recovery properties. Use of aprotic solvents for the DEAE-cotton-epichlorohydrin reaction gave finished cotton fabrics having only high wet wrinkle recovery properties.
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    Journal of Applied Polymer Science 13 (1969), S. 2333-2340 
    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 hydrazine hydrate with manganic hydroxide and its application to the solution polymerization of methyl methacrylate has been studied. The kinetic evidence suggests that the hydrazine and the monomer are both adsorbed on the surface of the manganic hydroxide sol and that the decomposition of the hydrazine and the polymerization of the methyl methacrylate follow zero-order kinetics. The rate of polymerization increases slowly with increasing temperature, the activation energy for the polymerization being 4.9 ± 0.2 kcal/mole.
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    Journal of Applied Polymer Science 13 (1969), S. 2383-2395 
    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 properties of 4-methyl-pentene-1 polymer (TPX-RT-D30) were altered by blending petroleum jelly (P.J.) with the polymer. The polymer was blended with up to 40% by weight P. J. The plasticization of the polymer by the P. J. apparently allows high molecular weight fractions of the polymer to crystallize and influences the crystalline size and perfection. Tensile properties of the blends showed both a break and yield value in all ratios as compared to only a break value for the pure polymer. Breaking strength ranged from 4000 psi for the polymer to 1000 psi at 40% P. J. The samples had a “necking down” effect at 10% P. J. Modulus decreased from 1.8 × 104 (literature value 2.1 × 105) to 2.3 × 104 at 40% P. J. Brittle point values varied from above room temperature to 5°C at 40% P. J. The Vicat softening point ranged from 181°C for the polymer to 87°C at 40% P. J. Differential thermal analysis (Stone) showed a melting point depression from 235°C to 218°C at 40% P. J.
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    Journal of Applied Polymer Science 13 (1969), S. 2439-2445 
    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: Curing reactions were investigated after the gel point, using infrared transmittance and reflection spectrophotometric techniques. In the system carboxyl-terminated polybutadiene (CTPB)/Epon X801 or Epotuf STF-6, catalyzed with Fe(III)-acetyl-acetonate (FeAA), at an equivalent ratio of carboxyl to epoxide groups, the final extent of reaction of COOH groups was found to be between 64% and 77% for eight CTPB samples. Increasing the ratio of epoxide to carboxyl groups (up to 1.6) resulted in an increase in the conversion, but the complete reaction of COOH groups could not be accomplished. The final extent of reaction also depends upon the functionality of the crosslinking agent. The lower the functionality of the epoxide, the higher the conversion of COOH groups. The use of chromium naphthenate as a catalyst for epoxide-COOH reactions gave higher conversions than FeAA. This result is related to side reactions catalyzed by the chromium naphthenate. The change in mechanical properties and the change in extent of reaction were followed simultaneously; it was found that no further development of mechanical properties occurred when the curing reaction between COOH and epoxide groups had ceased.
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  • 56
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    Journal of Applied Polymer Science 13 (1969), S. 2411-2425 
    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 conductivity, specific heat, and dynamic mechanical behavior of an epoxide system have been investigated over a relatively wide temperature range. Effects of nonstoichiometric amine concentrations and postcure heat treatments were included in the study. The thermal conductivity behavior was found to be related to the extent of cure of the poxy system, but in general the results were typical of an amorphous polymer. Calorimetric determinations were used to study the curing reaction and the glasslike transition temperature for the various systems. Dynamic mechanical results were employed to delinearte the various internal relaxations of the cured materials and in some instances to permit correlation of relaxations with the thermal conductivity and the specific heat results. From comparison of present results to those of a previous paper, the activation energy for the relaxation process occurring near 270°K has been estimated to be 16 kcal/mole.
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    Journal of Applied Polymer Science 13 (1969), S. 2459-2468 
    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: X-Ray diffractograms of cellophane showed a considerable variation in the intensity corresponding to the 101, 101, and 002 planes. Applications of generally accepted procedures for estimating crystalline content in cellulosic materials yields varying results for crystallimity in cellophane. It is concluded that such procedures are not applicable to cellophane used in this study.
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  • 58
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    Journal of Applied Polymer Science 13 (1969), S. 2499-2503 
    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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  • 59
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Long-term weathering studies of the subject transparent thermoplastic polymer revealed that sheets extruded from pristine resine gradually became hazy. Electron microscopy of fracture surfaces showed that minute voids were created during outdoor exposure. By the application of the Mie light scattering theory, it was possible to calculate that the average void size was 4 × 103 Å and that the concentration of voids numbered about 106/mm3. Yet the total void volume of the poorest sample, which had a haze value of 26%, was less than 0.05%. The average void size decreased over a three-year period, but the concentration increased with exposure. A mechanism of void formation was formulated based on photo-induced moleculàr degradation. Chemical evidence suggests that molecular degradation occurs by complete unzippering of a molecule, resulting in the formation of carbon dioxide and 2,2,4-trimethylpentene-3-al. The aldehyde is believed to plasticize the polymer in the vicinity of a growing void and the carbon dioxide acts as a blowing agent, therby generating a void. Simultaneously, free radicals formed during molecular decomposition initiate further degradation of neighboring molecules. The propensity of this resin to haze can be effectively overcome by suitable cleanup and stabilization procedures.
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    Journal of Applied Polymer Science 13 (1969), S. 205-213 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Molecular weight distributions for polypropylene samples have been determined by a permeation fractionation method (GPC). Porous silica beads were used as a packing material for the columns. The set of columns allows a good separation of the polypropylene macromolecular chains in a range of molecular weights from 5000 to 1.5 × 106, and the thermal and mechanical stabilities of these beads are very good. The calibration has been carried out with fractions of polypropylene of narrow molecular weight distribution prepared by a large-scale column fractionation. The molecular weights M̄w and M̄n and the ratios M̄w/M̄n calculated from the GPC curves show, in general, good agreement with the ones calculated from the column fractionation curves. However, the M̄w/M̄n ratios are always highter in the case of GPC fractionation. This could be due to diffusion phenomena.
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    Journal of Applied Polymer Science 13 (1969), S. 227-232 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: N-Substituted β-aminopropionhydrazides, RNHC2h4CONHNH2, were prepared by the Michael addition of primary amines to acrylic esters. The adducts were converted to the corresponding hydrazides. The aminohydrazides react readily with terminal epoxides at moderate temperatures yeilding B-stage resins of excellent storage stability. When powdered B-stage resins are sprayed on hot metal (150-230°C.), a smooth cross-linked coating is formed in less than 3 min. The coatings have unusually high elasticity, they pass the Olson button test. For best performance the amine used should have the primary amino group attached to either a primary carbon atom or directly to an aromatic nucleus. Aminohydrazides with the following R. Groups have been prepared: methyl, n-butyl, sec-butyl, tert-butyl, phenyl, cyclohexyl, benzyl, octyl, dodecyl, and octadecyl.
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    Journal of Applied Polymer Science 13 (1969), S. 249-250 
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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 13 (1969), S. 233-239 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Continued shearing of molten long-chain branched acetal polymers raises their melt flow rates manyfold. The increase is not due to molecular degradation, as evidenced by constancy of inherent viscosity, and by the ability to reverse the increase by dissolving and reprecipitating the polymer. Shearing was found to have only a relatively small effect upon the melt viscosity but a very large effect upon the entrance correction for capillary flow. It is suggested that crystallization of branched polymers from solution creates an exceptionally strong entanglement network, and that the observed rheological changes reflect the disruption by shear of this network.
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    Journal of Applied Polymer Science 13 (1969), S. 241-247 
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    Notes: Based on a simple, general kinetic scheme for the inhibition reaction of a photopoly-merizing system, a solution is obtained for the differential equation which describes the oxygen concentration profile as a function of exposure time, light intensity, and absorption coefficient. The effect of the absorption coefficient on the oxygen concentration in a polymer slab is evaluated by numerical computation.
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    Journal of Applied Polymer Science 13 (1969), S. 251-252 
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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
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    Journal of Applied Polymer Science 13 (1969), S. 2721-2733 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The influence of hydrogen bonding on the flow behavior of polymer melts at high shear rate has been investigated using a capillary extrusion rheometer. The systems studied were copolymers of ethylene and acrylic or methacrylic acid. Hydrogen bonding was found to substantially enhance both flow activation energy and viscosity level, as well as the degree of dependence of viscosity on rate of shear. It was also found that hydrogen bonding does not influence the critical shear stress for onset of “melt fracture.” The data support the view that hydrogen bonds act effectively as temporary (quasi-) crosslinks during the short time scales of deformation involved in flow at high shear rates.
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    Journal of Applied Polymer Science 13 (1969), S. 2705-2719 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Gamma radiation-induced graft polymerization to natural rubber in benzene solution (solution grafting), graft polymerization to natural rubber latex (Emulsion grafting), and emulsion polymerization of three vinyl monomers - styrene (St), methyl methacrylate (MMA) and acrylonitrile (AN), were carried out under air atmosphere to compare the radiation intensity exponent of each polymerization rate under air atmosphere with that under nitrogen atmosphere or under vacuum. The intensity exponents of the solution grafting both under air atmosphere and under exclusion of air were found to be numerals near one half. This indicates prevailing normal radical mechanism. However, the intensity exponents of the emulsion grafting under air atmosphere were found to be 0.94, 1.00, and 0.82 for St, MMA, and AN, respectively, and those of the emulsion polymerization under air atmosphere, 0.16 and 0.15 for St and MMA, respectively, although those of both emulsion grafting and emulsion polymerization under exclusion of air were found to be numerals near to one half except for that of emulsion polymerization of AN. For emulsion grafting, the initiating species is considered to be trunk polymer radical but the terminating species is assumed to be the radical(s) produced in the water phase in the presence of oxygen. For emulsion polymerization, both initiating and terminating species are assumed to be the radical(s) produced in the water phase in the presence of oxygen.
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    Journal of Applied Polymer Science 13 (1969), S. 323-336 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The oxidative susceptibility to different oxidizing agents such as dichromate-sulfuric acid, dichromate-oxalic acid and sodium hypochlorite in presence of leuco Cibanone Orange R of cellulose oxidized with sodium metaperiodate and its corresponding borohydride-reduced product was studied and compared with that of cellulose. From the changes in the chemical properties of the oxidixed products, an attempt was made to study the mechanism of oxidation of periodate oxycellulose and sodium borohydride-reduced periodate oxycellulose with the above mentioned oxidizing agents.
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    Journal of Applied Polymer Science 13 (1969), S. 377-391 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The extensive use of plastics for insulation and building materials has created interest in the possible toxicity of their combustion products. Three poly(vinyl chloride) homopolymers, a vinyl chloride-vinyl acetate copolymer, and formulations of two of the homopolymers and the copolymer have been examined to determine the composition and toxicity of their combustion products. Differential thermal analysis and thermal gravimetric analysis were used to study the breakdown process which occurred in several steps, the largest and first being the release of hydrogen chloride from the polymer at about 300°C. Approximately 50 products of combustion were then determined qualitatively by using either infrared spectroscopy or a combination of gas chromatography and mass spectroscopy. Quantitative analyses were carried out on 22 of the combustion products, and quantitative changes with varying air supply, temperature, and heating rate were determined. A comparison of the products of the polymers and their formulations is given.
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    Journal of Applied Polymer Science 13 (1969), S. 397-397 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Applied Polymer Science 13 (1969), S. 399-399 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 73
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    Notes: Thermogravimetric and differential thermal analysis have been employed to study the effect on the thermal degradation pattern in static air of the molecular weight of poly(m-aminostyrene) homopolymers and copolymers with styrene. Related substituted styrene polymers and copolymers with styrene have also been studied in order to assess the effect of introduction of amino, substituted amino, and hydroxy groupings into a polystyrene main chain. The effect of these groupings on the thermal stability of the polymers as compared with polystyrene suggests that the inherent antioxidant characteristics of the subtituent grouping plays the major role in stabilization. A molecular weight effect has been shown to be operative for m-aminostyrene, p-N,N-dimethylaminostyrene, and m-hydroxystyrene polymers. This manifests itself in terms of different thermograms rather than by significantly influencing the procedural decomposition temperatures, although a trend is seen.
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    Journal of Applied Polymer Science 13 (1969), S. 427-436 
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    Notes: The rate of contraction of drawn nylon 66 in aqueous phenol was investigated, and a method is described for correlating this contraction with a series of elementary rate processes. The rate constants so obtained were analyzed by absolute rate theory, and the variations of ΔH† and ΔS† with phenol concentration gave evidence of the nature of the reaction steps.
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    Journal of Applied Polymer Science 13 (1969), S. 561-570 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The kinetic model for polycondensation reactions has been derived and techniques for validating the model have been described in Parts I and II of this work. This paper is concerned with using the results of Part I and II for the analysis and design of continuous polycondensation reactors.
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    Journal of Applied Polymer Science 13 (1969), S. 571-576 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A tensile testing device for measurements on polymer samples while immersed in a liquid is described. The temperature range is approximately -100 to +150°C. The sample older containing the immersion liquid is an all-glass container attached to a modified tensile testing device. The thermostatting and recording equipment is also described. Stress-strain curves obtained with monofilaments of regenerated cellulose immersed in n-pentane and liquid ammonia are shown. For filaments in n-pentane the variation of the modulus of elasticity with temperature down to -40°C is also reported as a further example of the applicability of the new device.
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    Journal of Applied Polymer Science 13 (1969), S. 599-606 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effect of molecular weight on the changes in the surface layer of polystyrene films on near-ultraviolet irradiation has been studied in a nitrogen atmosphere at 25°C. Changes produced by irradiation were followed by determining the amount of solvent-insoluble portions, the molecular weight changes, and the intrinsic viscosity changes. Most crosslinking took place in the range of the transmissible depth of 2537 Å light. Low molecular weight samples formed a small amount of solvent-insoluble material. High molecular weight samples formed a large amount of solvent-insoluble material. In the range above a certain molecular weight, the amount of solvent-insoluble material approached an asymptotic value with increasing molecular weight, because of the limited penetration of 2537 Å light. Since most crosslinking took place in the range of the transmissible depth of 2537 Å light, the average number of crosslinks in the solvent-soluble portions was influenced by the amount of solvent-insoluble material. Low molecular weight samples produced many crosslinks. High molecular weight samples produced a few crosslinks. In the range above a certain molecular weight, the average number of crosslinks in the solvent soluble portions approached an asymptote with increasing molecular weight. Chain scission seems to have occurred in every sample.
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    Journal of Applied Polymer Science 13 (1969), S. 637-657 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Experimental data support the hypothesis that the surface layer of the asymmetric Loeb-Sourirajan type porous cellulose acetate membranes has a heterogeneous microporous structure. A general method is proposed for improving the performance of the above membranes in reverse osmosis, by which product rates are increased without decreasing solute separation. The method consists in pumping pure water past the back side of the membrane under just enough pressure for a sufficiently prolonged period of time; after such pretreatment, the membrane is used in the reverse osmosis experiments in the normal manner with the surface layer facing the feed solution. Back-pressure treatment at 400 psig for 85 hr on preshrunk and normally pressure-treated membranes increases the product rate by over 20% without decreasing solute separation in reverse osmosis experiments at 600 psig with the use of 0.5 wt-% NaCl-H2O feed solutions; with a different sequence of back-pressure treatment, similar results have been obtained in reverse osmosis experiments at 1500 psig also. The compaction effect of a normal membrane and that of a back pressure treated membrane are the same during continuous reverse osmosis operation under 600 psig; the effects of back-pressure treatment on a normal membrane and a compacted membrane are also the same. The pure water permeability data obtained in cyclic experiments show that the smaller pores on the surface layer are opened more than the bigger ones during the back side operation. The probable structural changes taking place in the film during back-pressure treatment are discussed.
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    Notes: The permeabilities of nitrogen, oxygen, and carbon dioxide through polyethylene-styrene graft copolymer films were measured by means of a gas permeability apparatus based on a modification of Barrer's high vacuum technique. Polyethylene-styrene grafts were prepared by mutual γ-ray irradiation of low-density polyethylene films in styrene-methanol solution. Densities and thicknesses of the graft copolymer films were determined. It was observed that the gas permeability constants decreased with increasing grafting to minimum values at 20-30% styrene grafting and increased again above 30% grafting. These results are explained in terms of a decrease in the free volume of the amorphous regions of the polyethylene by a “filling in” effect of the grafted polystyrene chains. Above 30% grafting, disruption of the crystallites may occur resulting in increased gas permeation. Activation energies for gas permeation through polyethylene-styrene graft copolymer films were calculated and found to decrease with increasing per cent styrene grafting. For nitrogen permeation, the activation energy decreased from 11.7 kcal/mole for unirradiated polyethylene to 9.5 kcal/mole for a 50.5% graft. Corresponding values for oxygen and carbon dioxide were 10.2-8.2 kcal/mole for a 48.7% graft and 8.4-6.5 kcal/mole for a 50.5% graft.
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    Journal of Applied Polymer Science 13 (1969), S. 713-720 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Chemical crosslinking of high-density polyethylene was studied. The amount of gel produced by a given peroxide concentration depends on the molecular weight of the polymer. More scission reactions, during the crosslinking process, occur in low-density than in high-density polyethylene crosslinked with Varox and Luperox 130 peroxides. The rheological behavior of partially crosslinked polyethylene is useful and convenient for quality control, for characterization, and for studies on the various mechanisms associated with the crosslinking process.
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    Journal of Applied Polymer Science 13 (1969), S. 775-784 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Present methods of correcting instrument spreading (resolution correction) in GPC are either too cumbersome to use or inaccurate when the correction is large. Two new methods which are both accurate and simple to use are presented in this work. The first method using the technique of Fourier analysis is more general and can be used to correct non-Gaussian instrument spreading. The second method using a fourth-degree polynomial requires a Gaussian instrument spreading function. The instrument spreading function may vary with respect to the elution volume in both methods.
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    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: Ruland's concept of an isotropic disorder function is applied to estimate the disorder parameter and the degree of crystallinity in a few cellulosic fibers: two cottons, native ramie, and a high-tenacity rayon. The results indicate an increase in disorder without any change in crystallinity on mercerization of native celluloses. On hydrolysis, with or without a pretreatment of mercerization, the samples exhibit a higher crystallinity, disorder remaining the same as for native celluloses. A ball-milled sample of “amorphous” cellulose is still found to be fairly crystalline with the lowest disorder. On being wetted in water and oven-dried, a distorted form of cellulose II with higher crystallinity and disorder was obtained. The polynosic fiber, Tufcel, has low values for the degree of crystallinity, disorder parameter, as well as crystallite dimension. A strong dependence of the degree of crystallinity on the crystallite size, particularly the lateral, is observed.
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  • 83
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    Journal of Applied Polymer Science 13 (1969), S. 807-816 
    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: Low temperature gaseous plasmas of ammonia or nitrogen-hydrogen mixtures contain —NH2 groups, or precursors thereof, formed in the plasma, which experimental evidence strongly suggests, can add to various polymer surfaces. The plasmas were established in the 0.3-1.5 torr range by radiofrequency (13.56 MHz) electrodeless excitation at powers ranging from 50 to 500 W. Samples of polypropylene, poly(vinyl chloride), polytetrafluorethylene, polycarbonate, polyurethane, and poly(methl methacrylate) were investigated. All these polymers added amino groups to varying degrees of amino site densities depending on the choice of plasma parameters and the reactivity of the polymer itself. In every instance the polymer was rendered more wettable, although no quantitative wettability measurements were made. Following the plasma treatment, degrees of amino attachment to the polymer were followed radiometrically and reported in terms of “heparin thicknesses” resulting from ionic heparin —35S attachment to quaternary sites produced from the amino groups. Two implications of such a surface modification are to adhesion and blood compatible materials preparation.
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  • 84
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    Journal of Applied Polymer Science 13 (1969), S. 817-826 
    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 molecular orientation acquired during fiber formation of acrylic fibers by wetspinning has been studied. Orientation was detected by measurements of sonic modulus which were converted into an orientation factor. The orientation correlates very well with the ratio of take-up velocity to the freely extreuded velocity. Several mechanisms for the origin of spin orientation are discussed.
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  • 85
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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: EPDM and SBR were masticated on an open mill. The temperature range of mastication for EPDM was 68-480°F. SBR was milled at 170-200°F. The gel-permeation chromatography analyses were made on the masticated samples. For EPDM at 68°F, molecular weight decreases and molecular weight distribution narrows with mastication time; the degradation process is nonrandom. At constant mastication time between 182 and 315°F, there is little change in molecular weight. Mastication for 18 min at 480°F broadens the molecular weight distribution; the degradation is random. For SBR at 170-200°F, molecular weight decreases and molecular weight distribution narrows with mastication time; the degradation process is also nonrandom. Nonrandom degradation for both EPDM and SBR results in a narrowing of the molecular weight distribution, without build-up of low molecular weight molecules, and without a shift in the peak molecular weight. This is contrary to nonrandom degradation of natural rubber where a shift in the peak molecular weight occurs with mastication time.
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  • 86
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    Journal of Applied Polymer Science 13 (1969), S. 827-833 
    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: Investigation of the nucleating ability of selected nucleating agents in various commercial types of isolactic polypropylene revealed that the efficiency of individual additives is not equal for all types of polypropylene. As to the nucleation mechanism, it can be supposed that in most cases the added nucleating agents act mainly secondarily, activating the heterogeneities originally present in the polymer.
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  • 87
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    Journal of Applied Polymer Science 13 (1969), S. 867-869 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We consider two approaches to strain magnification in a composite material, point out that they apply to different situations, and caution against misapplication of the equations derived.
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  • 88
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    Journal of Applied Polymer Science 13 (1969), S. 835-849 
    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: Latex dip adhesives for nylon and rayon tire cords are prepared by reacting resorcinol and formaldehyde in aqueous solution in the presence of a catalyst for a specified time and then adding a butadience-styrene-vinylpyridine latex. Ammonia improves the stability of the latex and increases the adhesion of rubber to cord. However, a white precipitate forms if ammonia is added before the resorcinol and formaldehyde have reacted sufficiently. This paper is study of the nature of this precipitate and the conditions for its formation. By measuring the heat of reaction of formaldehyde and ammonia and, subsequently, of mixtures of formaldehyde and resorcinol to which varying amounts of ammonia were added, information on the reaction mechanism has been obtained. Ammonia reacts rapidly with formaldehyde to form an unstable intermediate, presumably trimethylolamine, which then reacts further with resorcinol to form trisdihydroxybenzylamine. This compound is also very reactive and condenses withmore ammonia and formaldehyde to give a polymer of low solubility, the composition depending on the amounts of ammonia and formaldehyde available for reaction. Elemental analyses support this concept. Primary and secondary amines react in a maner similar to ammonia.
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  • 89
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    Journal of Applied Polymer Science 13 (1969), S. 851-865 
    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: Untreated and fire-retardant-treated white α-cellulose samples were isothermally pyrolyzed in a fluidized bath in a nitrogen environment at 298-360°C. Results were reported in terms of volatilization (based on weight loss-time measurements) and the degradation products (based on gas chromatographic-mass spectrometric analysis). The findings products (based on gas chromatographic-mass spectrometric analysis). The findings on untreated cellulose indicate that: (1) pyrolysis occurs in three distinct phases in the temperature range 276-360°C; (2) there is a single activation energy of 42 kcal/mole over this temperature range; (3) the initial rapid weight loss is not due to the desoprtion of water, but primarily to decomposition of the cellulose; molecules: (4) there is little difference in either the quality or relative quantity of the volatiles generated during the three different phases of pyrolysis. The findings on treated cellulose show that the fire retardant, KHCO3, does not markedly change the types of degradation products having molecular weights below about 110, althought it does change their relative concentrations. Furthermore, the rate of product generation and the quantity of residual char are increased.
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  • 90
    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-Versamid specimens were loaded in tension, compression, and flexure at different strain rates and temperatures to determine mode of failure, yield stress and strain, and tangent and relaxation moduli. Stress-strain curves were used to define brittle, ductile, ductile-rubbery, and rubbery modes of behavior which prevailed in different temperature-strain rate regions. The time-temperature superposition principle was applied to yield stress, initial tangent moduli, and relaxation moduli data for all three types of loading.The transition regions, tangent and relaxation moduli, and shift factors were the same in tension, compression, and flexure. Thus the most convenient mode of loading can be used to determine the general time-temperature dependence. The ratio of compressive-to-tensile yield stress was almost constant over the entire ductile region. Flexural yielding data were used to predict yield stress in tension and compression, and stress relaxation master curves were shown to be related to elastic modulus vs. strain rate curves. The yielding phenomenon was interpreted using Eyring's theory of non-Newtonian viscoplastic flow. The apparent activation energy and activation volume were larger for tension than compression. A theory is offered to explain why yielding can occur in a cross-linked system.
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  • 91
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    Journal of Applied Polymer Science 13 (1969), S. 1277-1288 
    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 development of new and more sensitive techniques in thermal analyses aids in a more complete understanding of the contributions of individual components in urethane elastomers regarding their mechanical and thermodynamic behavior. The behavior of various segments of the elastomers reported in this work illustrates a clearer interpretation of reasons for changes in mechanical behavior caused by changes in heat capacity, volume and tensile properties; the gross changes previously reported for polyurethane properties as a function of temperature are also confirmed with a more exact definition of their origin.The sub-ambient temperature behavior and response of physical measurements near the melting point of the backbone polyol are largely a function of the so-called “soft block.” The soft block does not contribute to the mechanical properties above the melting point of the polyol unless some urethane segments from the diisocyanate and extender are structured into the soft block, that is, excess diisocyanate and extender are added to build in the “hard” block. The extender and isocyanate influence for both low and high temperature properties is observed by the lack of molecular fit imparted to the backbone polyol as well as some crystallinity in the polymer hard block. The usual Tg transition reported in urethane elastomers corresponds to a first-order transition in the polyester or polyether backbone.
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  • 92
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    Journal of Applied Polymer Science 13 (1969), S. 1326-1326 
    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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  • 93
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    Journal of Applied Polymer Science 13 (1969), S. 1329-1335 
    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 effects of a number of sulfur compounds on the melt stability of polypropylene milled at 165°C have been studied. Dilaurylthiodipropionate (DLTP), Mercaptobenzimidazole (MBI), and Mercaptobenzthiazole (MBT) are all antioxidiants in a polymer lightly stabilized with a phenolic antioxidant although the last two are initially pro-oxidants. 2,2′-Dibenzoylaminodiphenyldisulfide (22BDD) is a pro-oxidant under the Conditions studied.In the absence of a phenolic antioxidant the effectiveness of DLTP is reduced in the early stages of oxidation, with increasing concentration although its over all antioxidant activity increases. The results are consistent with the view that both radical and non-radical processes occur concomitantly.
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  • 94
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    Journal of Applied Polymer Science 13 (1969), S. 1337-1351 
    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 preparation of the acetaldehyde polymers (PACH) having a poly(vinyl alcohol)-type structure and the thermal degradation of PACH have been reported previously. This paper will describe detailed aspects of several reactions of PACH. Copolymerization of PACH with toluene diisocyanate (TDI) was performed both thermally and catalytically. When piperidine was used as catalyst, the rate of reaction between PACH and TDI was found to depend on the concentration of both the active hydrogen of PACH and the isocynante group TDI. Acid and alkali treatment of PACH were carried out. On treatment with sulfuric acid, white polymers with good spinnability were obtained. The copolymerization of acetaldehyde with n-butylaldehyde were performed in the presence of sodium amalgam as catalyst. The reaction products were colorless, viscous liquids and assumed from the infrared and NMR spectra, elemental analyses, molecular weight and solubility tests to be aldol condensation-type copolymers.
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  • 95
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    Journal of Applied Polymer Science 13 (1969), S. 1353-1371 
    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 novel technique for the control of continuous synthesis of addition polymers with precisely controlled average molecular weight and minimum polydispersity has been developed. A control system adjusts the concentration of chain-transfer agent in the reactor feed to compensate for all other upsets, in the reactor inputs: initiator and monomer concentrations, temperature and feed rate. The technique has been evaluated quantitatively on a digital computer using a kinetic model of homogeneous, free-radical solution polymerization. In computational tests, the modeled control system generally held the instantaneous number-average chain length within 1%, and quickly returned it to the desired value in response to a wide variety of upsets. By generalizing the Schulz distributions to include termination by disproportionation, combination and chain-transfer, it is shown that changes in the molecular-weight distribution resulting from the action of the control system are minor.
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  • 96
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    Journal of Applied Polymer Science 13 (1969), S. 1381-1419 
    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-method of interpreting GPC chromatograms which accounts for skewing and symmetrical axial dispersion has been developed. General relationships for a symmetrical axial dispersion correction and for a skewing correction are derived.The method has been verified experimentally for unimodal chromatograms and linear calibration curves over a wide range of GPC operating conditions, polymer molecular weights and polydispersities. Measurements of h and skewing factors were obtained by a once-through technique. The need for performing reverse flow experiments has been eliminated. Artificial oscillations in the corrected chromatogram due to step size (Method of Pierce-Armonas), and to number of terms in a polynomial expansion (Method of Tung and Method of Smith) are eliminated.The method has yet to be evaluated for nonlinear calibration curves and multi-modal distributions. However, suggestions for its application in these circumstances are presented.
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  • 97
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    Journal of Applied Polymer Science 13 (1969), S. 1523-1535 
    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: Difluorocarbene (difluoromethylene, :CF2) generated by the pyrolysis of sodium chlorodifluoroacetate has been shown to irreversibly modify the surfaces of polymers and fibers. The critical surface tension values of several polymers are shown to decrease with increasing exposure to difluorocarbene vapors and ultimately approach the critical surface tension values of partially fluorinated polyethylenes. The rate-controlling step appears to be the diffusion of difluorocarbene from the precursor to the polymer substrate. The nature of the interaction between difluorocarbene and the polymer surface is unknown; however, the absence of infrared bands due to C—F bonds in attenuated total reflection measurements tends to establish the mono-molecular-like character of the modified surface.
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  • 98
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    Journal of Applied Polymer Science 13 (1969), S. 1509-1522 
    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: Study was made concerning both the rate of crosslinking and the structure of crosslinks of terpolymers that have dicyclopentadiene, 1, 4-hexadiene, methylene norbornene, and ethylidene norbornene for termonomers so as to look into the role of termonomers during crosslinking of ethylene propylene terpolymers. In the study, activation energy and frequency factor, both apparent were determined by the rate constant of crosslinking and differences in crosslinks were analyzed following both chemical and physical methods. Infrared analysis into the volume of consumption of double bond was adopted to examine the manner of crosslinking. In respect to the magnitude of the rate constant, ethylidene norbornene came in first being followed by 1,4-hexadiene, methylene norbornene, and dicyclopentadiene. The structure of termoners affected the apparent activation energy and the apparent frequency factor was subject to the influences of said structure and others including the variation in the degree of unsaturation. During the early stage of crosslinking, the formation of the crosslink of polysulfide-type was paramount to all others and the speed of conversion therefrom either to disulfide-type or to monosulfide varied with the kind of terpolymers and was in proportion to the rate constant of crosslinking.
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  • 99
    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 effects of crystalline modification of cellulose and of water on the ESR spectra generated by the trapped free radicals in gamma-irradiated celluloses were investigated for cotton cellulose I, II, III, and IV, partially decrystallized cotton cellulose, ballmilled cotton cellulose, hydrocelluloses of cellulose III and IV, and ramie. On irradiation of the celluloses, free radicals were formed on the cellulose molecule, probably following dehydrogenation or chain cleavage. The free radicals located within the less ordered or amorphous regions of the cellulose reacted readily with water and were terminated. The radicals located within the more ordered regions of the celluloses could be made accessible to reaction with water by the interaction of the celluloses with solvents which caused dimensional changes in the cellulosic structure. In the highly ordered regions of the celluloses, even after long periods of time in solvents which caused large dimensional changes in the cellulosic structure, the trapped free radicals were not terminated by reaction with solvent or water. The ESR spectra of the irradiated, dried celluloses were determined at -160°C, the single-line spectra recorded had line widths of about 18-24 gauss. On the absorption of water by the irradiated celluloses, the ESR spectra changed and were dependent on the crystalline structure of the irradiated celluloses. The effects of different arrangements of the irradiated celluloses, as shown by their trapped radical spectra, particularly after interaction with water, were discussed.
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  • 100
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    Journal of Applied Polymer Science 13 (1969), S. 1537-1544 
    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: Carbethoxycarbene, carbethoxynitrene, and nitrene generated respectively by the pyrolysis of ethyl diazoacetate, ethyl azidoformate, chloramine and sodium hydroxyl amine-o-sulfonate are shown to irreversibly modify the surface of polyethylene as shown by wettability measurements. The nature of the modification is not fully understood; however, insertion of the carbene or nitrene into a carbon-hydrogen bond appears likely. The modified surfaces thus formed are shown to undergo several classical organic reactions as again determined by wettability measurements.
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