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  • 1975-1979  (366)
  • 1920-1924
  • 1976  (366)
  • Chemical Engineering  (366)
  • 201
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 202
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 620-621 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 203
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 622-623 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 204
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. i 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 205
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 549-558 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Results are obtained permitting the systematic development of solution procedures for indexed equations by analyzing and combining a number of small problems. The solution procedures obtained are independent of index limits and can be written compactly by using nested FORTRAN DO-loops or equivalent. To illustrate the approach, a solution procedure is developed for a multistage, multicomponent distillation column segment. The solution procedure is valid for any number of stages and components.
    Additional Material: 9 Ill.
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  • 206
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 564-568 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The operating theory of the gas centrifuge is developed under both steady and unsteady state behavior. It is shown that countercurrent flow patterns in a gas centrifuge enhance the possible separation. The effect of self-diffusion of the gaseous mixtures is shown to be significant with low molecular weight gases but of less significance with heavy gases such as uranium isotopes. The time required to develop steady state pressure and concentration profiles is in the order of minutes, even with no net flow to and from the machine.
    Additional Material: 3 Ill.
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  • 207
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 590-592 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 208
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 594-597 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 209
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 603-604 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 210
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 607-610 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 211
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 691-695 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Comparison of solute concentrations at the outlet of a model dialyzer with values calculated from the appropriate convective diffusion equation yielded effective diffusion coefficients for mass transfer of sodium chloride in sherared suspensions of 37 to 74 μ spheres of a copolymer of styrene-divinylbenzene. Significant mass transfer augmentation was observed over that attributable to molecular diffusion, and the effective diffusivity increased with increasing concentration of suspension but remained relatively constant with respect to shear rate over the experimental range.
    Additional Material: 6 Ill.
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  • 212
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 772-779 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A liquid flowing over a nonwettable surface can form rivulets of various types. The regime of rectilinear rivulet flow plays a key role in that it provides the basis for the study of the other regimes.An analytical solution for the velocity distribution of rectilinear rivulet flow down a vertical plate is derived. A generalized Ritz-Galerkin method is used to obtain a polynomial solution for the case of an inclined plate.These results, unlike those of previous authors, enable one to calculate all the rectilinear flow properties of rivulets over the complete range of practical interest.
    Additional Material: 7 Ill.
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  • 213
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 759-765 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A four-parameter corresponding states method with the critical temperature, the critical pressure, the radius of gyration, and a fourth parameter developed from the Frost-Kalkwarf vapor pressure equation has been applied to the correlation of liquid heat capacities. An equation has been developed to predict the temperature dependence of the saturated liquid heat capacities of both normal and polar fluids over the liquid range from a reduced temperature of 0.35 to 0.96. The accuracy of the predictions obtained is superior to that of the presently available generalized correlation for polar liquids. The new correlation may be easily adopted for computer use.
    Additional Material: 3 Ill.
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  • 214
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 779-785 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The utility of electropolarization chromatography for fractionation of native protein mixtures is examined both mathematically and experimentally.Mathematical prediction based on a simplified but basically realistic model of this process suggests it to be very promising for both analytical and preparative purposes.This expectation is borne out by tests with well-defined proteins in single ultrafiltration fibers. The major observed departure from model prediction is an unexpectedly sharp increase in retardation at a critical voltage specific to the protein and composition of the carrier electrolyte. This permits sharper separations than previously expected and is thus favorable.
    Additional Material: 8 Ill.
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  • 215
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 701-713 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A predictive kinetic model has been developed for fluid catalytic cracking (FCC). The kinetic scheme involves lumped species consisting of paraffins, naphthenes, aromatic rings, and aromatic substituent groups in light and heavy fuel oil fractions. The kinetic model also incorporates the effect of nitrogen poisoning, aromatic ring adsorption, and time dependent catalyst decay. The rate constants for these lumped species are invariant with respect to charge stock composition. The predictive capabilities of the model have been verified for wide ranges of charge stocks and process conditions.
    Additional Material: 19 Ill.
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  • 216
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 942-944 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 217
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 218
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 959-960 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 219
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 979-984 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The limiting current technique is used to obtain mass transfer coefficients at very low Reynolds numbers (Re 〈 0.1) in a packed bed consisting of stainless steel spheres. The data show that for Re 〈 0.015, the Nusselt numbers are below those predicted by existing empirical correlations. The results are discussed in the light of some mathematical models for packed beds reported in the literature and show semiquantitative agreement with the values predicted by Sorensen and Stewart (1974a).
    Additional Material: 2 Ill.
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  • 220
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    AIChE Journal 22 (1976), S. 1006-1012 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Solubilization rates of fatty acids in pure detergent solutions are controlled by mixed micelle desorption and diffusion. Solubilization rates in partially saturated detergent solutions also involve exchange of fatty acids between the solid and the solution. These conclusions depend on models like those used in gas-solid catalysis and in tracer diffusion.
    Additional Material: 7 Ill.
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  • 221
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    AIChE Journal 22 (1976), S. 1027-1032 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The modeling equations formulated for a catalytic packed-bed reactor with distributed resistance to flow have been applied to the alumina catalyzed isomerization of 1-butene to cis- and trans-2-butene. Flow maldistribution was deliberately created in a 5.25 cm I.D. reactor by packing different radial sections with alumina particles of different size. Effluent gas composition, monitored by gas chromatography, was found to vary with radial position in a manner consistent with the modeling equations and with the reaction rate constant previously established in a microreactor.
    Additional Material: 7 Ill.
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  • 222
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    AIChE Journal 22 (1976), S. 1055-1063 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equilibrium staged batch parametric pumps are studied with nonlinear isotherms. The half cycle is composed of one single equilibration step and one discrete transfer. The limiting regime (for infinite number of cycles) is shown to correspond to a staircase construction between the two isotherms, the number of steps being equal to the number of stages. The reservoir concentrations are then connected by Fenske's equation. Several analogies with binary total reflux distillation are suggested.
    Additional Material: 11 Ill.
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  • 223
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    AIChE Journal 22 (1976), S. 1090-1096 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The presence of internal circulation in forming liquid drops has a significant effect on mass transfer rates. For the systems studied, no circulation was observed below a Reynolds number of 9.7. For Reynolds numbers between 9.7 and 34.4, transition from zero circulation to complete circulation during the entire drop formation period occurred. In studies on the rate of mass transfer from fixed volume drops with forced internal circulation, increases in mass transfer rates were found at Reynolds numbers which corresponded to those observed for the development of internal circulation patterns within the drop.
    Additional Material: 6 Ill.
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  • 224
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 1145-1147 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Tab.
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  • 225
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    AIChE Journal 22 (1976), S. 1152-1155 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 226
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 22 (1976), S. 894-904 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new tracer technique is reported for the determination of liquid-solid contacting efficiency and liquid holdup in trickle beds packed with small alumina particles. Holdup was a function of liquid mass velocity for both porous and nonporous packing. Contacting efficiency remained uniform at a level of 65%.
    Additional Material: 10 Ill.
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  • 227
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    AIChE Journal 22 (1976), S. 940-942 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 228
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    AIChE Journal 22 (1976), S. 1021-1027 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Through the statement of the vectorial form of the Ergun equation, combined with a differential component balance, a formulation was developed describing the velocity fields and reactant concentration profiles in an isothermal packed-bed reactor in which the gas flow is nonuniform. This flow maldistribution was caused by both the preferential flow near the wall, inherent in most systems, and by the deliberate arrangement of the solid packing in the bed. The numerical solution of the governing equations showed that a nonuniform flow field had a very strong effect in distorting the concentration isopleths, particularly at intermediate conversion levels.
    Additional Material: 6 Ill.
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  • 229
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    AIChE Journal 22 (1976), S. 1050-1055 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 230
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    AIChE Journal 22 (1976), S. 1079-1090 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Prospects for enzymatic synthesis processes on an industrial scale depend upon development of a practical process for ATP regeneration. The relative merits of various routes to ATP regeneration involving chemical synthesis, whole cells or organelles, or cell free enzymes are evaluated. The most promising route involves one or more enzyme incorporating the reaction catalyzed by acetate kinase for ADP phosphorylation.
    Additional Material: 1 Ill.
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  • 231
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 59-64 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 migration of phthalate plasticizers from poly (vinyl chloride) into edible oils has been analyzed. The principal method used involved 14C-labeled dibutyl and dioctyl phthalates with detection by liquid scintillation spectrophotometry. In most cases, the migration of the main plasticizer was accompanied by the migration of the secondary plasticizer, when present, and by diffusion of the oil into the polymer. Comparison of the scintillation results with those obtained by weight loss measurements can give quantitative information on the amount of the liquid medium that diffuses during the migration process. The effect of the following factors on the migration process was examined; (a) the nature and acidity of the edible oil, (b) the composition and amount of phthalate plasticizer, (c) the amount of epoxy plasticizer, and (d) the temperature and time of contact.
    Additional Material: 3 Ill.
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  • 232
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    Polymer Engineering and Science 16 (1976), S. 65-73 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Although polymeric materials have a relatively minor role in our solid waste disposal problems, they display a particular prominence as litter because of their environmental permanence, Photodegradation has been suggested as one possible solution, but considerable debate has centered on the need, costs, and limitations of such degradable systems. The chemical mechanisms involved in practical photodegradation are illustrated by a review of the oxidation schemes for normal and sensitized polystyrene. The different mechanisms associated with the use of additives, comonomers, and halogens are considered in some detail. A listing of patent literature relating specifically to photodegradable polystyrene is included in the review.
    Additional Material: 2 Ill.
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  • 233
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    Polymer Engineering and Science 16 (1976), S. 294-297 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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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  • 234
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    Polymer Engineering and Science 16 (1976), S. 303-308 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 synthesis, processing characteristics, thermal propers, and adhesive and composite properties of polyphenvlqmnoxahnes are briefly reviewed. In addition, new high molecular weight soluble carbonate/phenylquinoxaline copolymers from the cyclopolycondensation of aromatic bis(o-diamines) with a bis(benzilyl) carbonate are reported.
    Additional Material: 1 Ill.
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  • 235
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    Polymer Engineering and Science 16 (1976), S. 298-302 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Examples are given to show how molecular structures may be synthesized to prepare polymers useful for the formation of fibers intended for specific end uses, particularly for high performance applications. Current trends and developments taken from the literature are reviewed and some new work from the laboratories of Monsanto Company is presented concerning the use of aromatic polymers for heat and flame resistant fibers. Some new polymers and new routes of synthesis are described. Correlations are made between flame resistance as measured by oxygen index (O.I.) values and the structure of a large number of aromatic polymers.
    Additional Material: 2 Ill.
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  • 236
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    Polymer Engineering and Science 16 (1976), S. 490-495 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two kinds of thermodynamic theories, which seem to be applicable to polymer deformation and flow, have been developed in the recent literature. One of these approaches utilizes entropy far from equilibrium as a primitive undefined concept. The alternate kind of theory involves the idea of a quasi-static process as a primitive concept. In this work, an approach based on internal state variables (specifically, the micro structure of the polymeric material) is used to argue that both primitive concepts are in some sense legitimate on physical grounds. In particular, the legitimacy of the quasi-static process concept is related to the smoothness of the function delivering the rate of change of the microstructure.
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  • 237
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    Polymer Engineering and Science 16 (1976), S. 480-489 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 apparatus has been constructed to measure the thermal conductivity and the thermal diffusivity of reactive and nonreactive liquids and solids. The method used consists in suddenly subjecting the test specimen to a thermal flux and measuring the velocity of the heat wave across the sample. Maintaining the heat flux leads to a steady thermal gradient across the sample from which the thermal conductivity can be determined. The test duration is short relative to durations employed by existing conventional techniques and thus causes only a small thermal disturbance to the sample of the order of 1 to 2°C. Thermal properties of liquids and solids, including thermoplastics and a typical epoxy resin during cure with different equivalents of an aromatic diamine hardener have been measured near room temperature. Experimental data compare favorably with literature values for similar systems. Variations in thermal conductivity and diffusivity during cure have been obtained through a series of individual discrete measurements to cover the whole isothermal cure history. The results have been analyzed and discussed with respect to the cure characteristics of the resin and the nature of the physicochemical changes the material undergoes during cure.
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  • 238
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    Polymer Engineering and Science 16 (1976), S. 507-509 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In a previous paper, results of morphological studies using electron microscopy and X-ray diffraction were reported concerning random and non-random olefin copolymers of ethylene. As comonomers, relatively low concentrations of n-alpha alkenes and 5-methyl norbornene-2 were used. It was tentatively concluded that one possibility for morphological changes observed in the n-alpha alkene copolymers was a change in direction of chain folding. These studies have been continued with copolymers of ethylene and acenaphthylene. The intent was to pursue effects of vicinal substitution; however, the result was to produce ethylene copolymers of quite high comonomer content which were crystalline and showed no evidence of an independent beta mechanical transition. Further, definite evidence was found to indicate a change in the direction of chain folding in the polymer crystals.
    Additional Material: 4 Ill.
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  • 239
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    Polymer Engineering and Science 16 (1976), S. 496-506 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Incompatible blends comprised of polystyrene and various high density polyethylenes were processed into tapes, in which both the phase and molecular orientations were parallel to the machine direction, by a combination of extrusion and mechanical stretching of the melt prior to quenching. Machine direction tensile yield strengths and ultimate elongations were found to be considerably higher than those obtained for comparable compression molded samples throughout the range of blend compositions and processing conditions investigated. Transverse tape properties were consistently poor due to poor interfacial adhesion. An optimum in machine direction properties was observed as the stretch ratio was increased at various melt temperatures. This optimum is likely due to a competition between morphological and molecular orientation rates during the stretching process and is a complex function of stretching rate and melt temperature as well as blend composition, relative phase viscosities, polyethylene crystallinity, and interfacial adhesion. Tapes stretched at high melt temperatures tended to show decreasing ductility and increasing tensile strength as room temperature storage time increased. This is believed to be due to secondary crystallization of the polyethylene phase. Oriented tapes were found to be easily fibrillated by mechanical heating to form a pulp. This material may prove suitable as a high grade replacement for cellulose pulp in paper making and could be formed at low cost from waste plastic feed stock.
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  • 240
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    Polymer Engineering and Science 16 (1976), S. 510-511 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Polyolefins are generally known either as partially crystalline thermoplastics or as elastomers. With the finding in the ethylene-acenaphthylene copolymer system of the unusual properties of high crystallinity, high modulus, and no independent beta thermomechanical transition at high comonomer contents, it appeared that it might be possible to prepare a block polymer system which would retain the desirable low temperature transition near -110°C and “hard” acenaphthylene copolymer segments as well. Attempts were made, and the resulting terpolymer is described. An intermediate crystallinity polymer of apparently broad composition distribution was obtained with the modulus of high density polyethylene but the elongational characteristics of low density polyethylene.
    Additional Material: 1 Ill.
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  • 241
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    Polymer Engineering and Science 16 (1976), S. 559-563 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 great strides made over the last two decades allow the design engineer to predict performance characteristics in solid plastics. The current state of the art in structural foam is somewhat more primitive. Theories and basic design procedures as well as measurement of mechanical properties require evaluation. Because of the deep penetration of structural foam into the marketplace, especially in the large consumer areas of furniture and automotive applications, design techniques are required to cover the many application. This paper reviews briefly the basic information needed for structural foams, compares empirical relations and theoretical models, and discusses some inherent limitations of foamed materials.
    Additional Material: 9 Ill.
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  • 242
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    Polymer Engineering and Science 16 (1976), S. 564-566 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Stringent government environmental regulations applied to the electroplating industry have spurred a search for alternative means of providing chromium coatings on plastics. Vapor deposition, an established and extensively utilized process for applying aluminum coatings on plastics, is quite naturally being investigated as an alternative process. Vapor deposited chrome has a darker cast than electrochrome, and a great-number of materials are being investigated to find a color matching substitute that will stand up under severe environmental conditions. Among these are the 300 and 400 series stainless steels, nichrome, and other alloys. It has been found, with proper surface preparation, that highly adherent and specular stainless steel coatings/can be obtained oh plastics using filament and boat evaporation techniques. The coatings resemble a highly polished version of the parent metal and bear a striking resemblance to chrome. However, some type of clear topcoat is required to provide abrasion resistance.
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  • 243
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    Polymer Engineering and Science 16 (1976), S. 735-741 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Almost all polymer processing operations involve moving and shaping the polymer as a melt and then cooling it, usually quite rapidly, to a solid state. In order to develop models for such processes we have begun systematic studies in non-isothermal rheology; here we interpret the results in the context of melt spinning. Theoretical predictions of stress vs distance from the spinneret were calculated from generalized (non-isothermal) viscoelastic theory and compared with Dees' melt spinning data on high density polyethylene. Despite certain experimental and theoretical difficulties, the agreement is good. Surprisingly, an additional theoretical curve, based on a simple Trouton viscosity, also gave a reasonable approximation over much of the distance, despite the transient nature of the flow. To understand this phenomenon further, a more tractable theoretical problem was studied in detail; the problem, of constant elongational flow (Ė = constant) in the presence of a constant rate of temperature change (dT/dt = constant). The results depend on two dimensionless groupings; the first is the usual product of a relaxation time and Ė; the second involves the ratio of normalized dT/dt to Ė. When the second group is large, a quasi-viscous state exists. The melt spinning data for the HDPE may be near this state.
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  • 244
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 Part I paper described the mechanochemical basis for achieving high adhesive strength in bonds between polymeric surfaces such as polyethylene, polypropylene, and Teflon, using the SABRA method (Surface Activation Beneath Reactive Adhesives). This paper gives a brief survey of bonding techniques as well as results of shear tests of simple lap joints and scarfed tube joints. They compared favorably with other methods such as CASING, Peeling test results are also presented. Mixed systems were examined such as glass fiber reinforced polyester bonded to polypropylene and aluminum with thin films of polymeric material sandwiched between. A start was made towards of optimization and exploration of primer specificity for different materials, The implications and further applications of the SABRA method are discussed.
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  • 245
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    Polymer Engineering and Science 16 (1976), S. 771-776 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 blends over extended compositional ranges have beer, prepared for combinations of a thermoplastic urethane elastomer with polystyrene, a styrene-acrylonitrile copolymer, a polyhydroxyether (Phenoxy A), and poly(vinyl ethyl ether). The thermoplastic urethane elastomer was based on a polycaprolactone diol of approximately 2100 number average molecular weight, 4,4′-diphenylmethane diisocyanate and 1,4-butanediol at a molar ratio of 1/2/1, respectively. At ambient temperature, the tensile properties of the blends typically are intermediate between the values of the two separate components. Characterizations of the dynamic mechanical properties of the blends show the relative degree of compatibility for the thermoplastic urethane elastomer and the respective polymers. Two separate glass transitions are obtained for blends of polystyrene and the styrene-acrylonitrile copolymer with the thermoplastic urethane elastomer. This behavior demonstrates that these blend systems are incompatible. The blends of Phenoxy A and the thermoplastic urethane elastomer exhibit a single glass transition for which the temperature is dependent on the respective concentration of the components. These mixtures are considered to be compatible in nature.
    Additional Material: 4 Ill.
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  • 246
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    Polymer Engineering and Science 16 (1976), S. 785-791 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Plates of bisphenol-A polycarbonate and poly(methyl methacrylate) have been quenched in ice water from temperatures slightly above their glass transition temperatures. Residual stresses are thus created, Measurement of these residual stresses has been accomplished by the “layer removal” method and the stress distributions through the thickness are presented. Compressive stresses, approximately 3000 psi, exist at the surface while tensile stresses-of at least 1000 psi exist in the interior. It is shown that these residual stresses can influence the notched Izod impact strengths for polycarbonates. The mechanism is thought to be suppression of craze initiation in advance of the notch due to the presence of residual compressive stresses for specimens notched prior to quenching. In the case of poly(methyl methacrylate), it is shown that compressive residual stresses at the surface can cause plastic yielding to occur in bending experiments resulting in permanent deformation and greater energy absorption.
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  • 247
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    Polymer Engineering and Science 16 (1976), S. 817-820 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In spite of the availability of- almost fifty commercial synthetic plastics, many new ones were announced at the recent First Chemical Congress of the North American. Continent at Mexico City. Among these are the high temperature resistant aramides and imides, poly(phenylene sulfide), poly(phenylene oxide), poly(aryl sulfone), H resin, modified phenolic resins and the phosphazenes. Other new polymers are block and graft copolymers, conductive polymers, barrier resins, poly 1,2-butadiene, polyolefins and polyurethanes. New coupling techniques and shortages of feed stocks have resulted in a renewed interest in filled plastics and recycled polymers.
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  • 248
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: PVC plastisols were formulated with silicone surfactant, mechanically shipped to form froths, and oven-fused to form open-cell foams. These were much softer than conventional chemically-blown foams which contain mixtures of open and closed cells. Increasing plasticizer content and decreasing foam density also had the expected softening effects on foam properties.
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  • 249
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    Polymer Engineering and Science 16 (1976) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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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  • 250
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    Polymer Engineering and Science 16 (1976), S. 1-10 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 history of PPO®, polymers of 2,6-dimethylphenol, and Noryl® resins is described from the initial discovery through commercialization. The scope of oxidative polymerization as applied principally to phenols and acetylenes is outlined as well as the chemical reactions which can be performed on the resulting polymers.
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  • 251
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    Polymer Engineering and Science 16 (1976), S. 74-81 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of thermal annealing and quenching on the notched Izod impact strength of several polymers has been studied. Primary emphasis was placed on polycarbonate, but ABS, PVC, polysulfone, and polymethylmethacrylate were also studied. It was determined that residual stresses created by thermal quenching from above the glass transition temperature can have a great effect on impact strength for the polycarbonate, PVC, and polysulfone polymers studied. In fact, it is shown that the thickness transition observed in impact strength for polycarbonates is governed by the residual stresses and not by thickness. In polycarbonates, quenched sheets up to 3/8 in. in thickness have shown impact strengths of 18 ft-lb/in. whereas sheets 1/8 in. in thickness can be embrittled by annealing, showing an impact strength of 2 ft-lb/in. However, it has been shown that this embrittlement results from the absence of residual stress. Residual stresses having maximum values up to 3000 psi (in Compression) have been determined at the polycarbonate sheet surface using birefringence measurement techniques. The existence of these compressive stresses is postulated to restrict the extent of craze growth at the notch tip, and the impact specimen can yield rather than fail in a brittle manner if the stress state is sufficient.
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  • 252
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    Polymer Engineering and Science 16 (1976), S. 87-92 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Polymer blends and composites are composed of two different components, and usually, two different phases. Sometimes one phase is continuous and the other clearly discontinuous. Often, however, both phases retain some degree of continuity, as in certain fiber reinforced composites, block copolymers, materials composed of alternating lamellae structures and interpenetrating networks. A semi-empirical theory is developed to express mathematically not only the known structures, but also two-phase morphologies not yet synthesized or characterized. Many structures both real and proposed are shown to exhibit dual phase continuity, although for most systems, one phase can be said to be “more continuous” and the other “less continuous”.
    Additional Material: 4 Ill.
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  • 253
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    Polymer Engineering and Science 16 (1976), S. 82-86 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: For fabrication processes such as blow molding, vacuum forming, film blowing and fiber spinning, extensional flow is the dominate mode of melt deformation. Under these conditions, extensional viscosity is a significant rheological property. Thus, the biaxial extensional viscosity was measured for several samples of polypropylene. A technique based on the bubble inflation method of Denson and Gallo was used. Experimental values of biaxial extensional viscosities ranging from 1014 to 1010 poise as a function of strain rate, 10-5 to 10-2 reciprocal seconds, were obtained at 25°C. The technique used was critiqued and found to be useful in characterizing unoriented and biaxially oriented films, Uniaxially oriented films gave unsatisfactory results. It may be possible to use this testing method to assist in materials selection decisions.
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  • 254
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    Polymer Engineering and Science 16 (1976) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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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  • 255
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    Polymer Engineering and Science 16 (1976), S. 93-100 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Chlorinated PVC is superior to unmodified PVC as a thermoplastic for use in thermoforming, especially if improved heat resistance and dimensional stability are required. In the present report, results tire given of a fundamental experimental study on the thermoformability of CPVC sheets obtained by calendering various formulations based on CPVC resins with at least 65 percent chlorine content. Extensibility as well as the relationship between stress and strain in uni- and biaxial stretching have been determined as a function of temperature and rate of stretching by means of specially devised, highly instrumented laboratory equipment. Stress-strain relations under isothermal conditions and at constant strain rate are compared for the two modes of stretching, and the difference in behavior between PVC and CPVC, particularly with regard to the effect of temperature, is emphasized. Internal stresses frozen in during cooling, following rapid stretching at appropriate thermoforming temperatures, have been determined by means of a detailed analysis of retractive force measurements. The relationship between internal stress and molecular orientation is discussed as well as the effect of the latter parameters on various properties of technological interest: dimensional stability, impact resistance, and gas permeability.
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  • 256
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    Polymer Engineering and Science 16 (1976), S. 101-116 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 computer study was made to determine the thermal ignition criteria and ignition boundaries for chain-addition polymerization in a well-mixed batch system using a simple kinetic model. The occurrence of thermal runaway was shown to be a function of initiator type, feed conditions, and heat transport parameters. It was found that thermal runaway does not occur early with respect to monomer and initiator conversions and that for strongly dead-ending systems, the sensitivity characteristic of ignition disappears. The role of various dimensionless parameters in characterizing reaction behavior is also discussed.
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  • 257
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    Polymer Engineering and Science 16 (1976), S. 117-123 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Thermal runaway arid parametric sensitivity were experimentally demonstrated in styrene polymerizations. Ignition boundaries were established for several initiator concentrations and a dimensionless boundary plotted. Runaway sensitivity was shown to disappear under specific conditions.
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  • 258
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    Polymer Engineering and Science 16 (1976), S. 125-125 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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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  • 259
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    Polymer Engineering and Science 16 (1976), S. 126-137 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 elongation and orientation of randomly coiled macromolecules in a strained melt or solution reduces their entropy and thus increases the crystallization or melting temperature of the ideal lattice. At any given temperature of experiment this enhances nucleation and crystal growth rate. As a rule, linear primary nuclei are formed. They contain more or less extended chains. The existence of row nuclei reduces the local gradient in the liquid to such an extent that further crystallization proceeds by epitaxial overgrowth of folded chain lamellae. Densely packed cylindrites are formed with the ribbon-like lamellae radiating from the central row nucleus. The irregular shish-kebab structure observed in stirred or sonicated solutions seems to be formed by subsequent exial deformation of cylindrites in the flow field. It displaces the lamellae irregularly and thus produces a great many microfibrillar elements parallel to the original row nuclei. The almost completely extended chains in the shish yield a high elastic modulus and tensile strength for exial loading. The shish-kebab morphology in fibers as spun does not affect to a great extent the mechanical properties obtainable by subsequent drawing. The lamellae are transformed into microfibrils in very much the same manner as in spherulitic samples. But the highly regular orientation of lamellae seems to result in a more uniform drawing and hence a stronger fiber. In an extremely high temperature and pressure gradient, the melt extrusion produces hard elastomers where the lamellae of the cylindrites seem to be locally stapled. Upon application of tensile load in the extrusion direction, the intervening sections bend like beams, thus forming thin holes extending in the direction perpendicular to the load. The holes enormously enhance the permeability for gases and liquids. The elastic bending of lamellae yields the high recoverable strain and low tensile modulus.
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  • 260
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    Polymer Engineering and Science 16 (1976), S. 158-162 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Several observations are made regarding the role of the fluid mechanics involved in the process of flow-induced, fibrillar crystallization from solution. Computational evaluation and discussion of various flow effects in the nucleation step, including combined shear and extensional flows, are presented in terms of the elastic dumbbell model. These results indicate the important role extensional kinematics in the growth process. A qualitative evaluation of concentration effects is also given. The evaluation of facts concerning the growth morphology is presented in terms of a model for the growth process along with data concerning rinsing and quench rate effects on the morphology and inciting behavior of shish kebab crystals.
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  • 261
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    Polymer Engineering and Science 16 (1976), S. 168-175 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 theory of crystallization under stress is developed about the premise that the direction a chain takes through a crystallite, relative to its end-to-end vector, is determined by the first few links of a chain that initially deposit onto the crystallite surface. Since these few links are quickly trapped by subsequently crystallizing chains, their orientational probability prior to deposition governs the chain direction through the crystallite, and the properties of the system depend upon a statistical distribution of all vector orientations. Such a model leads to a relationship between the melting temperature and the degree of network orientation, and relates the retractive force to temperature in the crystallization region. The theory appears to adequately describe some of the published data on rubber and polychloroprene networks.
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  • 262
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    Polymer Engineering and Science 16 (1976), S. 163-167 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 theory of the stress-induced crystallization of polymeric networks is presented which takes into account 1) the free energy of fusion, 2) crystal surface energies and 3) entropic changes in the amorphous sections of crystallizing chains. It is assumed that the vector running from one end to the other of the crystallite is oriented in the direction of network extension, irrespective of crystal morphology, thus minimizing the free energy of crystallization. Assuming that the network assumes the crystal morphology which minimizes the free energy of the network at a given degree of crystallinity and that the crystallization proceeds along this lowest free energy path, it is predicted for simple network extension that growth of a perfectly oriented extended-chain crystal occurs initially, changing to a one-fold crystal oriented perpendicular to extension at low extension and to a two-fold crystal having nearly perfect orientation at High extension. The stress is predicted to decay initially and then to rise as the network chains switch from an extended-to a folded-chain morphology. Spatial factors which may trap chains in the ex tended-chain morphology or prematurely stopping the crystallization process can result in a mixed crystal morphology. At high extension, the structure is similar to that of the shish kebab.
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  • 263
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    Polymer Engineering and Science 16 (1976), S. 176-181 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Injection molded hinges of polypropylene possess uniquely unlimited flex life. Polypropylene when crystallized from the melt under extensional flow (as in injection, molded hinges), shows a unique morphology characterized by a planar row structure of lamellae accompanied by a bimodal distribution of the unit cells having the alpha crystal phase. This bimodal orientation consists of two apparently independent orientations of the unit cells with respect to the flow direction: one with the c-(chain) axis parallel to and one with the a′-axis parallel to the flow direction. (The a′-axis is a vector normal to (100) and thus parallel to a* in reciprocal space.) Experimental data on the morphology of polypropylene crystallized under extensional flow are interpreted in terms of two components. The c-axis component corresponds to those molecules in the planar row structure. The a′-component is attributed to secondary crystallization in which small crystallites are finely dispersed between the lamellae of the row structure. These small crystallites act as a “morphological plasticizer” protecting the load-bearing row structure from destructive stress during flexure.
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  • 264
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    Polymer Engineering and Science 16 (1976), S. 182-188 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 crystallization behavior of samples of poly(ethylene oxide) of varying molecular weights and molecular weight distributions has been studied under varying conditions of shear rate and temperature. These experiments have been carried out in two devices. One is a shearing parallel-plate instrument that allows direct observation of the crystallizing medium. The other is a shearing concentric-cylinder dilatometer. In general, shear enhanced the rates of crystallization and nucleation. However, conditions were encountered under which shear retarded crystallization and/or nucleation. Combination of the data from these two devices suggests that, under certain shearing and sample conditions, chain slippage and particle fracture lead to decreased apparent rates of nucleation and/or crystallization.
    Additional Material: 15 Ill.
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  • 265
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    Polymer Engineering and Science 16 (1976), S. 204-211 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 study demonstrates that it is possible to extrude highly oriented polyethylene fibers using only a plasticating single screw extruder, specially designed and operated dies, and a simple take up mechanism. The degree of orientation achieved is as high as that achieved in solid state extrusion studies but accomplished at a fraction of the pressure. The degree of orientation is significantly greater than that of commercial grade fibers. The orientation is developed in the elongational flow of the “wine glass stem” region preceding the die entrance and is retained by crystallization in the die. Crystallization is inhibited in the pre-die region by maintaining a temperature above the effective melting point of the flowing, oriented (hence lowered entropy) melt.
    Additional Material: 15 Ill.
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  • 266
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    Polymer Engineering and Science 16 (1976), S. 200-203 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 on the effects of molecular weight on the physical and mechanical properties of cold-extruded high density polyethylene. Prior data indicate that such ultra-drawn strands contain a significant fraction of extended-chain crystals. Four samples, spanning the molecular weight range of 59,000 to 147,000, were cold-extruded under the same conditions and were examined with respect to their melting point, degree of crystallinity, linear expansion coefficient, Young' modulus, strain to break, and tensile strength. The degree of crystallinity, linear expansion coefficient, and modulus did not change significantly with molecular weight. The melting point, strain to break, and tensile strength do increase with increasing molecular weight. This leads to the conclusion that the amount of extended-chain crystals is invariant with molecular weight. Higher molecular weight polymers are seen as providing a greater number of the chains, thus giving the fiber a higher tensile strength.
    Additional Material: 4 Ill.
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  • 267
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    Polymer Engineering and Science 16 (1976), S. 189-199 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 principles of rheology are applied to the study of the shear-induced crystallization of molten polymers. A new technique is described for measuring crystallization kinetics during isothermal flow at constant shear rate in a parallel plate rheometer. The crystallization rate is characterized by the time elapsed from the start of shearing until the rise in melt viscosity due to crystallization. The measured-viscosity and induction time for crystallization are shown to be independent of sample geometry. Kinetic data are presented for crystallization of three linear polyethylenes at shear rates of 0.03 - 30 sec-1. It is shown that shear flow has a strong accelerating effect on crystallization when the deformation rate exceeds a critical value. Comparison of results for the different polyethylenes reveals that higher molecular weight materials crystallize faster at a given shear rate and temperature. Finally, shear-induced crystallization of propylene polymers is shown to be unaffected by the presence of either a carbon black additive or a heterogeneous nucleating agent. It is concluded that the hydrodynamic origin of the shear-induced crystallization is elastic chain extension due to entanglement couplings between molecules. Furthermore, it is suggested that transient orientation effects during the startup of shear flow may have a dominant influence on the observed phenomena.
    Additional Material: 14 Ill.
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  • 268
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    Polymer Engineering and Science 16 (1976), S. 240-245 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is described to predict the time-temperature behavior and hence thermal stability of PVC melts in a Brabender Plasticorder torque rheometer from basic rheological data(flow and thermal stability observations) obtained on an Instron capillary rheormeter. The predicted and experimentally determined values of the Brabender thermal stability are shown to be in good agreement.
    Additional Material: 10 Ill.
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  • 269
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    Polymer Engineering and Science 16 (1976), S. 323-326 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four new poly functional amines were synthesized. Polyimide films containing varying amounts of the amine crosslinking agents were prepared. Their thermomechanical properties were compared with those of control film samples prepared from difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperature is discussed.
    Additional Material: 3 Ill.
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  • 270
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    Polymer Engineering and Science 16 (1976), S. 318-322 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Polyphenylquinoxalines (PPQ) were crosslinked with a tris-benzil comonomer, to alleviate the inherenthigh temperature thermoplasticity, and evaluated as matrices in graphite reinforced composites. The room temperature flexural strength/modulus of Modmor IJ laminates were as high as 245,000 psi/16,6 × 106 psi. Essentially 100 percent retention of ambient mechanical properties was obtained at 371°C using a PPQ matrix from the fully-crosslinked polymer prepared from 4,4′-bis(4″-oxybenzilyl) benzil (BOBB) and 3,3′-diaminQbenzrdine. The degree of high temperature thermoplasticity in the composite was found to be more closely related to the final postcure temperature than to the BOBB crosslink density. The thermoplasticity essentially disappeared when the BOBB comonomer-PPQ laminates were postcured at 482-510°C in nitrogen. Substitution of DMAC for the commonly used m-cresol solvent system allowed facile preparation of prepreg to fabricate low-void laminates and NOL rings.
    Additional Material: 5 Tab.
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  • 271
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    Polymer Engineering and Science 16 (1976), S. 327-333 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: By combining quantitative molecular, microscopic and macroscopic information from an oriented crystalline polymer, it becomes possible to unify, predict, and explain not only processing behavior but such important material properties as failure, shrinkage, modulus, yielding, melting, and storage and loss moduli. Among the advantages gained by this approach are the ability to: (a) identify the particular phase of the two-phase system which controls a given property-(b) correlate internal structure quantitatively with a large number of seemingly different types of properties; (c) identify quantitative behavioral rules which are generally valid for Very different crystalline polymers; (d) clarify component roles such that new techniques and processes result; and (e) predict the properties of a crystalline polymer for structural states not previously tested. Using two dissimilar crystalline polymers, isotactic polypropylene and poly(ethylene terephthalate), as examples, the general validity and unifying power of the structural approaches is demonstrated.
    Additional Material: 16 Ill.
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  • 272
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    Polymer Engineering and Science 16 (1976), S. 334-343 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Constitutive relationships are presented to relate the directional dependence of the mechanical properties of anisotropic, partially crystalline polymers to (a) the percent crystallinity, (b) characteristics of the crystalline and amorphous orientation distribution, and (c) the mechanical properties of the crystalline and amorphous components. These relationships were tested with structural and dynamic mechanical data obtained for isotactic polypropylene films in various states of crystalline and amorphous orientation. The dynamic mechanical properties of the crystalline and amorphous components were treated as parameters and evaluated from dynamic mechanical measurements along the longitudinal and transverse direction of three different film samples. These mechanical parameters, and the associated structural parameters, were in turn used to predict the dynamic mechanical spectra for a fourth, independent, film sample. The predicted values for the storage and loss modulus, along various directions of loading, were within 10 percent of the measured values over the temperature range of -80°C to 80°C.
    Additional Material: 8 Ill.
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  • 273
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    Polymer Engineering and Science 16 (1976), S. 344-352 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 Halpin-Tsai equations are based upon the “self-consistent micromechanics method” developed by Hill. Hermans employed this model to obtain a solution in terms of Hill's “reduced moduli”. Halpin and Tsai have reduced Hermans' solution to a simpler analytical form and extended its use for a variety of filament geometries. The development of these micromechanic's relationships, which form the operational bases for the coniposite analogy of Halpin and Kardos for semi-crystalline polymers, are reviewed herein.
    Additional Material: 4 Ill.
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  • 274
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    Polymer Engineering and Science 16 (1976), S. 353-356 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Experimental examination by torsional braid analysis (TEA) of the phenomena of gelation and vitrification which occur in the formation of thermosets leads to a general way of regarding both thermoplastics and thermosets. In particular,- it is demonstrated that the thermosetting process is characterized by two transition temperatures, Tff and Tg∞. Implications of this finding are discussed for cross-linking systems in general.
    Additional Material: 5 Ill.
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  • 275
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    Polymer Engineering and Science 16 (1976), S. 357-360 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 Tll (〉Tg) transition in amorphous poly-styrene by the technique of torsional braid analysis is reviewed. For the most part, the relaxation behaves like the glass transition (Tg) in its dependence on molecular weight, on average molecular weight in binary polystyrene blends, and on composition in a compatible plasticized system.
    Additional Material: 9 Ill.
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  • 276
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    Polymer Engineering and Science 16 (1976), S. 365-370 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Regions in which the mechanical and dielectric properties of polymers change rapidly with temperature (transitions or relaxations) are supposed to be due to the onset of certain types of molecular motions. A precise description of these various molecular motions would be invaluable in the areas, of structure vs property relationships and the tailoring of polymers to end-uses. However, our knowledge concerning these motions is quite limited and qualitative at best. The biggest stumbling block has been an inability to test the consequences of proposed mechanisms in terms of experimentally observed quantities. The problem in many cases has not been a lack of adequate theory but rather an insufficiency of knowledge, appropriate for input into the theory, concerning the energetics of chain motions. However, in the past few years there has been considerable progress in studying chain energetics by means of conformational energy calculations (molecular mechanics). In the present paper, this work on crystalline polymers will be reviewed and some recent calculations which illustrate the present state of the art are discussed.
    Additional Material: 7 Ill.
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  • 277
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    Polymer Engineering and Science 16 (1976), S. 361-364 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Conformational energy calculations on poly(2-vinylimidazole) (PVI) and poly (2-vinylbenzimidazole) (FBI) indicated that the syndiotactic polymer would exhibit systematic intramolecular hydrogen bonding between side groups along the chain, while the isotactic polymers could not. This fact, together with our previous wor.k using solvent effects to produce highly syndiotactic poly(methacrylic acid) during radical polymerization, indicated that similar techniques could be applied in the radical polymerization, of 2-vinylimidazole and 2-vinylbenzimidazole. These mpnomers were polymerized over a wide temperature range using cobalt 60 gamma radiation as the initiator. The conditional probabilities obtained from NMR spectra of these polymers could be fit by second order Markov statistics (FBI) and extended second order Markov statistics (PVI). The difference reflects the effect of the bulkier benzimidazole side group. The nature of the conditional probabilities needed to fit the data for PVI suggest that the stereoregularity depended on the number of consecutive terminal r placements at the end of the growing radical. A marked solvent effect was observed was attributed to the hydrogen bonding strength of the solvent and its ability to disrupt the r directing polymer hydrogen bonding.
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  • 278
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    Polymer Engineering and Science 16 (1976) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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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  • 279
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    Polymer Engineering and Science 16 (1976), S. 371-387 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 four-stage synthesis of molecular, micromechanical, and macromechanical models is used to predict the dependence of the longitudinal and transverse Young's moduli and the axial and transverse shear moduli of anisotropic polyethylene on percent crystallinity and the state of molecular orientation. Variational methods are employed to establish the upper and lower limits for anisotropic elastic response. The difference between lower and upper bound limits is interpreted as the potential for improving mechanical performance. A modified form of the Tsai-Halpin equation is used to examine parametric ranging (via a contiguity factor, ξ) between the lower and Tupper bound limits. In this application, the contiguity factor is interpreted as a characteristic of the internal stress-strain distribution which is dependent upon the size, shape, packing geometry, and elastic properties of the crystalline and amorphous regions. The potential for achieving high modulus polymeric materials is illustrated by treating percent crystallinity, molecular orientation, and contiguity as materials design variables subject to control by processing conditions. Optimum property trade-offs, necessary for balancing the over all mechanical behavior of anisotropic materials, are illustrated through the control of orientation and contiguity, The theoretical predictions for the moduli of anisotropic polyethylene are in good agreement with values reported for material processed by traditional procedures as well as ultra-oriented polyethylene.
    Additional Material: 10 Ill.
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  • 280
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    Polymer Engineering and Science 16 (1976), S. 389-393 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Polyphenylene oxide was surface-sulfonated with chlorosulfonic acid to provide antistatic properties. Optimal treatment time was shown to be 2-3 mins with a saturated solution of the acid in hexane or 25-30 mins using acid vapor-saturated air under the given experimental conditions at room temperature. Being sensitive to humidity, the resistivity of the treated surface was lowered to the magnitude of 107 to 108 ohm/square at 43 percent relative humidity and to 1011 at 10 percent relative humidity. The vapor phase method was found to be superior to the solution method with respect to the durability of the treated surface against water washing. Microscopic examination revealed extensive surface erosion by the solution treatment.
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  • 281
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Calculation of the elastic constants of a participate composite material in terms of the elastic constants of the filler and the matrix is discussed. The theories of Kerner or Hashin and Shtrikman, the equivalent theories of Budiansky and Hill, and a generalized van der Poel type theory are presented and discussed. Data from several sources are compared with the predictions of these theories. The van der Poel theory provides the best agreement and gives good values for volume fractions of filler up to 0.35.
    Additional Material: 4 Ill.
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  • 282
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    Polymer Engineering and Science 16 (1976), S. 400-405 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The rate and temperature dependent fracture behavior of glass-filled polystyrene has been investigated over the crack speed range of 1013 to 1 mm/sec and in the temperature range 283 to 396°K for three environmental conditions: (i) air; (ii) water; and (iii) hot water exposure at 363°K and subsequent drying. Relationships between fracture toughness (Kc), crack speed and temperature have been obtained experimentally and analysed according to the concepts of fracture mechanics and reaction rate theories. Crack propagation in air is shown to be controlled by a β-relaxation process associated with crazing. Activation energies of 200 ∼ 210 kj/mole in air and 80 ∼ 120 kj/mole in water are reported. At a given temperature and crack speed, the glass-filled polystyrene is shown to display smaller crack propagation resistances in a water environment when compared with the air results. Specimens subjected to hot water exposure and then tested after drying also possess less cracking resistance. This toughness degradation phenomenon is a result of the damaging effects of the water which penetrates into the glass-filled composite.
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  • 283
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 paper describes a computer software package applying a steady-state hill-climbing optimization routine to the plastics melt-extruder screw constrained-design problem. The purpose primarily is to introduce the optimal screw-design technique, to show how it is applied to this particular type of problem, to indicate its potential and to encourage its wider use. Screw performance criteria are defined by a theoretical model consisting of the non-Newtonian isothermal polymer flow equations in terms of the screw-geometric variables for particular process conditions. The design method is quite general however and a non-isothermal model may be substituted. Use of the method offers considerable scope and potential for the design engineer to make design processes faster, more positive and logical while reducing the effort required. Interactive use is possible and empirical adjustments can be incorporated with experience. In using the method, the design engineer first specifies the required process conditions of pressure and flow rate at the die and the computer then searches for the set of screw design variables which optimizes the screw power utilization efficiency or any other specified criterion of performance. Such optimal designs are obtained within the set limits of practical constraints on machine dimensions, screw strength and product quality requirements. Some experimental evidence is given relating to the accuracy of the isothermal non-Newtonian polymer flow model and to its use in the design of small diameter extruder screws. The optimal search technique offers considerable potential as a computer-based design tool.
    Additional Material: 14 Ill.
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  • 284
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    Polymer Engineering and Science 16 (1976), S. 450-462 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 residence time distribution (RTD) function in a single screw plasticating extruder was theoretically calculated. The calculation is based on the solids conveying, melting, and melt conveying models in extruders. The screw channel is divided into small axial increments and the path of each exiting fluid particle is followed from hopper to die. In addition to the residence times the total shear deformation or strain imposed on the fluid particles was also calculated. This together with the RTD function has led to the definition and calculation of the strain distribution function (SDF). This function is proposed for quantitative characterization of the mixing performance of screw extruders as well as other laminar mixers. Some simple idealized batch and continuous laminar mixers are analyzed in terms of the SDF. Finally, the effect of extruder operating conditions and screw design on the RTD and SDF were investigated by computer simulations.
    Additional Material: 15 Ill.
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  • 285
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    Polymer Engineering and Science 16 (1976), S. 465-472 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of annealing on the microstructure of commercial grade poly(vinyl chloride) was investigated by calorimetric, X-ray and viscoelastic measurements. The degree of crystallinity increases with increasing annealing temperature from above the glass transition temperature up to 130°C, at which point the degree of crystallinity takes on a maximum value. Also, the crystal melting temperature increases with increasing annealing temperature. Thermal analysis and X-ray study suggest that the crystallite of poly (vinyl chloride) decomposes by thermal degradation when annealed, above 170°C. The isothermal crystallization process is analyzed using Avrami's equation employing the degree of crystallinity as a function of annealing time at various annealing temperatures. The crystallization rate has a maximum value at around 140°C. It is expected that the crystalline texture grows in the shape of a lineal-like habit, judging from the magnitude of Avrami's constant and from a study of the X-ray intensity distribution. The αf-transition was observed to occur at temperatures 5 to 10°C lower than the crystalline melting temperatures for annealed specimens of poly(vinyl chloride) using a dynamic spring analysis. The αf-transition may be attributed to thermal molecular motions with a long time scale, resulting from the cross-link points introduced by the small crystallites.
    Additional Material: 14 Ill.
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  • 286
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    Polymer Engineering and Science 16 (1976), S. 473-479 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 chemistry of p-xylelene and of its analogues has been reviewed. Its modes of formation and polymerization to poly-p-xylelene have been described, and the initiation and hypothetical termination steps have been discussed. The reactions taking place in the gas phase and in the deposited film are contrasted with those taking place in solutions. The problems of crystallization of the polymer simultaneously proceeding with its growth have been stressed. Finally, the properties of poly-p-xylelenes and their application in the coating industry have been described in some detail, emphasizing the special advantages of gas-deposition leading directly to a solid and coherent film. Some future fields of application of this technique have been outlined.
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  • 287
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    Polymer Engineering and Science 16 (1976), S. 602-608 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Experiments are described which show that stresses in amorphous polymers can be measured by diffracting X-rays at high Bragg angles from a filler consisting of crystalline particle or powders. The method is applicable, when calibrated, to both applied and residual stresses, to stress relaxation studies, to both tensile and compressive stresses, to both interior and surface positions in an object, and to composites of various types as well as to polymers that are substantially homogeneous. In the lower (Hookian) range, strains and stresses in metallic embedded particles increase linearly with applied stresses and strains in the matrix. When applied stresses exceed an apparent yield point, which correlates with the yield strength of the metallic filler, the elastic strains in the particles increase only slightly or even decrease as the matrix strains are increased, and with constant applied strain, the particles reveal changes due to relaxation. Strains in the particles are found to be smaller, and stresses higher, than in the matrix. Tests of graphite-fiber epoxy composites with embedded filings of silver or aluminum alloy show that compressive residual stresses from curing at 350°C and cooling to room temperature are registered in the particles as well as stresses externally applied to the cured composite. Precision of the order of 1000 psi (0.7 kg/mm2 or 6.9 M Pa) was obtained with measurements made and evaluated rapidly and simply; with more refined techniques, much higher precision would be possible.
    Additional Material: 5 Ill.
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  • 288
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    Polymer Engineering and Science 16 (1976), S. 615-625 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 of a solid or gas filled polymer is used in processing or end use application calculations. Numerous theoretical and empirical correlations are found in the literature. A careful review of these models indictes that no one correlation or technique accurately predicts the thermal conductivity of all types of composites. The investigation indicated that for solid filled composites the Lewis and Nielsen equation fitted the experimental data best for the range of fillers tested. However, for a gas filled polymer, none of the theoretical models proved adequate. The semi-empirical approach of Harding showed considerable merit.
    Additional Material: 6 Ill.
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  • 289
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 609-614 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Characteristics of the fracture of fiber reinforced plastic composites are described in terms of the elastic stress distribution at the crack tip, the mechanism of crack tip damage, and the modes and conditions of final fracture. The three-dimensional, stress field at the tip of a sharp crack in a laminate is presented and contrasted to traditional two-dimensional models. The response of the material in the form of inter- and intraply damage formation and growth under increasing load is characterized, and its effect in blunting the main crack is examined. The final fracture conditions, which may range from quasi-brittle to notch insensitive, are discussed and related to the damage zone extension. Observed and anticipated effects of various material and geometric parameters are also discussed.
    Additional Material: 7 Ill.
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  • 290
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 626-637 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 extensive set of rheological data, including steady shear, normal stress, and oscillatory response functions, have been obtained for several polyethylene melts, and a modified form of the Spriggs nonlinear co-rotational model has been used to represent the data. The resulting model was used to predict the transient stress response of the melts in a simplified model of the extrusion process, with a resulting criterion for the onset of melt distortion in terms of readily evaluated rheological parameters. The predicted occurrence of melt distortion based on this criterion agreed well with observations for the polymers in this study as well as for a variety of other polymers reported in the literature.
    Additional Material: 11 Ill.
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  • 291
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 292
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 680-686 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 description of the fluid mechanics and the energy transfer mechanisms present in a liquid rotational molding system is discussed. A simplified model assuming the liquid can be drawn off in a continuous layer over the mold surface was assumed. For the case of a negligible energy of reaction, a closed form analytical solution has been developed. The effects of mold composition and polymer thickness on the heating and cooling cycles have been analytically determined. The more complex problem, which includes the energy of reaction, has been solved for a representative case.
    Additional Material: 10 Ill.
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  • 293
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 discussion of the basic mechanisms and governing laws for liquid mixing is used to motivate new design concepts for more efficient mixing equipment. In this part of the paper, the use of V-grooves in the inner cylinder of a concentric cylinder mixer is examined. The purpose of the grooves is to induce vortex-like motions in the fluids in order to overcome the negative effects of interface orientation on mixing performance. Results show that the grooves are efficacious in increasing the effectiveness of the mixer. Descriptions of the experimental and analytical work done to characterize the design and to prove its efficacy are presented in detail. Scale-up parameters are also discussed.
    Additional Material: 11 Ill.
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  • 294
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 721-724 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Following the discovery that linear polyethylene can be drawn to very high draw ratios to produce oriented fibres and films with ultra-high initial moduli, a similar study has been undertaken for polypropylene. In particular, the modulus/draw ratio relationship has been obtained for a range of polymers of different molecular weight and molecular weight distribution. The effects of thermal history and draw temperature were studied, and it was shown that under optimum conditions material with an initial modulus at room temperature of 1.9 × 1010 Nm-2 (205 gdtex, 3 × 106 psi) can be obtained. This value is at least 50 percent greater than those previously recorded for drawn fibres and about one half of the theoretical modulus.
    Additional Material: 6 Ill.
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  • 295
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 734-734 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 296
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 725-734 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Linear crystalline polymers can be processed to high degrees of orientation sufficient to produce dramatic increases in tensile strength and modulus. Three processes have been identified for inducing such orientation: cold drawing, hydrostatic extrusion, and solution spinning. All three processes utilize a high elongational velocity gradient in a critical temperature range to produce a high strength crystalline morphology. Although the molecular superstructure may differ in each case, the mechanical properties are similar, An increase in strength is achieved either through the creation of new tie molecules between crystal lamellae or through the creation of an extended chain crystal substructure. Temperature and molecular weight are the prime variables in determining which morphology will develop. The optimum processing temperature for many of the specific techniques is the crystalline dispersion temperature. At this temperature, the crystal structure is particularly adaptable to forming a new crystal morphology. Ul-tradrawn polymers are more Hookean in behavior than isotropic polymers and have properties similar to steel and glass. Polyoxymethylene has been processed most closely to its theoretical strength. Polyethylene, which is the most difficult to process, has achieved the highest modulus of any common polyolefin polymer, about 7 × 1010 Pa.
    Additional Material: 6 Ill.
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  • 297
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    Polymer Engineering and Science 16 (1976), S. 742-746 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Mold flows and melt viscosities of an incompatible bi-component EPDM and “Viton” fluoroelastormer system were examined. A marked reduction in the melt viscosities of either component was observed when a small amount of the other component was present. It was speculated that the phenomenon was a result of a slippage between the polymer and the coated capillary surface due to the presence of a minor amount of the incompatible polymer. Evidence is given to indicate that this effect cannot be accounted for using the “melt structural heterogeneity” mechanism proposed for a different system by Andtrianova.
    Additional Material: 4 Ill.
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  • 298
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 technique for improving the strength of bonded joints between various materials and different adhesives is described. Increased strength was obtained by mechanical Surface Activation Beneath Reactive Adhesives (SABRA). This technique results in higher bond energies due to the creation of free radicals. The surfaces were activated by abrasion with emery paper in the presence of the adhesive itself (epoxy), or of some suitable primer such as methyl methacrylate, acrylonitrile (AN) or hydrogen sulfide gas. The effects of this technique were demonstrated by four different methods: 1) Improved wetting of standard epoxy or water drops on the treated surface. 2) Achievement of bond energies between primers and polymeric surfaces exceeding the energy of solution in solvents, which were revealed by attenuated total reflectance infrared. 3) The detection of free radicals created by bond scission during abrasion by means of diphenylpicryl hydrazyl, (DPPH), a free radical scavenger, monitored by spec-trocolorimetry, 4) Destructive testing of single lap joint test Pieces, scarfed tube joints and pee) test samples. These experiments will be described in a second paper. The theoretical base of the new approach is supported by a tentative estimate of energies set free by mechanochemical creation of free radicals and the excess heat released during abrasion.
    Additional Material: 13 Ill.
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  • 299
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976), S. 777-781 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 stress-strain behavior of a material exhibiting Andrade creep (for which the creep compliance is linear in the cube-root of time) has been calculated for loading at constant strain rate \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm \varepsilon}\limits^{\rm .} $\end{document} and at constant stress rate \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop \sigma \limits^. $\end{document} for the limiting case of linear viscoelastic behavior and at constant \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop \sigma \limits^. $\end{document} for one type of nonlinear viscoelastic response. The recoverable strain after the stress has been removed has also been calculated for these three cases. The results of the calculations are compared with experiment.
    Additional Material: 5 Ill.
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  • 300
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 16 (1976) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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