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  • 1990-1994  (7,413)
  • 1985-1989  (6,639)
  • 1830-1839
  • Biochemistry and Biotechnology  (7,216)
  • Chemical Engineering  (6,836)
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  • 1
    Electronic Resource
    Electronic Resource
    Polyspirodilactam: A new family of high temperature polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 6-11 
    Details
    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 class of materials based on a spirodilactam structure has been recently synthesized as part of research into new polymeric materials. Not only is the spirodilactam structure novel, but it was not even the intended product in the synthesis as originally designed. The polymerization process discovered by the reaction of 4-ketopimelic acid or its corresponding spirodilactone with primary amines opened a new field of polysprodilactam chemistry. This paper describes the chemistry leading to the discovery of spirodilactam-based polymers and initial applications in the area of thermoplastics and thermosets. Most recent developments to be covered include aromatic spirodilactams and isomeric spirodilactams.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340105
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  • 2
    Electronic Resource
    Electronic Resource
    High temperature thermosets based on the cocuring of a novel spirodilactam bisallylether and bismaleimide (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 12-16 
    Details
    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: Spirodilactam bisallylether is a new high temperature performance monomer. It melts at 154°C, and is thermally inactive in forming a homopolymer. However, it reacts readily with a bismaleimide via “ene” reaction. Therefore, it could be used as a comonomer and an effective toughening modifier for bismaleimide. The properties of the blends of spirodilactam bisallylether and 4,4'-bismaleimidodiphenyl-methane were studied. The cocured resins have high glass transition temperature, 〉 300°C. By adding 30 to 40 mole % of the bisallylether, the compact tension toughness of the bismaleimide was improved to 0.7 MPa-m1/2. Therefore, the resins have a combination of high glass transition temperature and toughness. They also showed good flexural properties. Despite the high water absorption, 5 to 7%, the resins retained high hot/wet flexural properties because of the high glass transition.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340106
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  • 3
    Electronic Resource
    Electronic Resource
    Compatibilization of immiscible blends with a mutually miscible third polymer (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 59-68 
    Details
    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 immiscible blend systems, styrene-maleic anhydride/styrene-acrylonitrile (SMA/SAN). styrene-maleic anhydride/acrylonitrile-butadiene-styrene (SMA/ABS), poly(vinylidene fluoride)/SAN (PVF2/SAN), and PVF2/ABS, were investigated. The effect of adding up to about 10 wt% of a third polymer that is miscible with each blend component, poly(methylmethacrylate) (PMMA), was determined. In every case, the addition of PMMA led to the improvement of properties such as tensile strength, tensile elongation, and notched impact strength. Furthermore, the addition of PMMA resulted in finer, more uniform dispersions of the primary blend components. The experimental results are interpreted in terms of interfacial activity of the common phase component, PMMA.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340111
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  • 4
    Electronic Resource
    Electronic Resource
    A thermoanalytical study on solid-state cure of poly(p-phenylene sulfide) (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 81-85 
    Details
    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: Differential scanning calorimetry (DSC) was used to investigate the solid-state cure process of poly(phenylene sulfide)(PPS) resin. Virgin PPS resin in an open sample pan was cured in DSC cell. Either air or oxygen was used as a curing atmosphere. Cure temperatures were in the range of 200 and 250 °C, which are below the melting point of PPS resin. Cure temperature as well as atmospheric condition influenced the cure behavior of PPS in the solid state. Both the rate and the amount of cure increased with increasing cure temperature. On the other hand, the time to reach the maximum cure rate was independent of cure temperature. Changing the atmosphere from air to oxygen increased both the cure rate and the amount of cure. The size effect of PPS particles on the cure reaction was also discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340202
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  • 5
    Electronic Resource
    Electronic Resource
    The anisotropy of slow crack growth in polyethylene pipes (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 109-115 
    Details
    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: Slow crack growth was measured in the perpendicular and parallel directions relative to the extrusion direction of the pipe. For five pipes from different manufacturers, the anisotropy factor, the lifetime to fracture in the perpendicular direction divided by lifetime in the parallel direction, varied from 1.2 to 4.7 for complete fracture and 1.4 to 4.0 for crack initiation. The degree of molecular orientation was determined by measuring the shrinkage that occured when a pipe specimen was heated near its melting point. The amount of shrinkage correlated with the anisotropy factor for slow crack growth. The shape change after shrinkage was related to the flow pattern of the resin during extrusion and the cooling rate after extrusion.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340206
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  • 6
    Electronic Resource
    Electronic Resource
    Viscoelasticity of some engineering plastics analyzed with the modified stress-optical rulePart 7 of the series “Birefringence of Amorphous Polymers.” (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 135-140 
    Details
    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 complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, EG*(ω) and ER*(ω); the modified stress-optical coefficient, CR and CG, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, CR, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, CG, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, EG*(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, ER*(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340210
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  • 7
    Electronic Resource
    Electronic Resource
    A closer look at the MWD-viscosity transform (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 159-165 
    Details
    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: While there is abundant evidence that the molecular weight distribution (MWD) of a linear polymer has an influence on the shape of the viscosity function, the ability to convert the viscosity function to an MWD has been questioned. Using strictly numerical techniques, we have shown that the viscosity function can be transformed to the MWD, but always with some distortion. However, distinct bimodality can be qualitatively preserved through both the MWD-viscosity and viscocity-MWD transforms.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340213
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  • 8
    Electronic Resource
    Electronic Resource
    A model for the unfoamed skin on microcellular foams (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 169-173 
    Details
    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 microcellular plastics, an unfoamed skin that is integral with the foamed core can be created by allowing the nucleating gas to diffuse from the surfaces of a gas saturated specimen prior to foaming. In this paper, a semi-empirical model is proposed that predicts the skin thickness variation in microcellular foams as a function of gas desorption time. The model shows good agreement with experimental results on the polycarbonate-carbon dioxide system.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340302
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  • 9
    Electronic Resource
    Electronic Resource
    Kinematics and deformation characteristics as a mixing measure in the screw extrusion process (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 174-189 
    Details
    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 present paper proposes “Deformation Characteristics” (DC) as a new deformation measure of screw extrusion processes, based on the Green deformation tensor. In contrast to previous strain measures heuristically proposed by Mohr, et al., Mckelvey, and Pinto and Tadmor, the new DC can naturally incorporate the demixing phenomena and systematically take into account the three-dimensional circulatory flow with the screw flight effect. Therefore, DC can be regarded as an improved strain measure. “Weighted Average Deformation characteristics” (WADC) is also proposed to indicate the overall deformation characteristics as a quantitative measure to the “goodness of mixing” of the extrusion process. The present paper includes discussion on delicate differences between DC and several other strain measures in case of the two-dimensional velocity approximation, and on the application of DC into a general three-dimensional velocity field obtained by a quasi-three-dimensional finite element analysis of extrusion processes. In determining WADC in the three-dimensional application, the residence time distribution function, including the three-dimensional circulatory flow effect, is used.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340303
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  • 10
    Electronic Resource
    Electronic Resource
    Simulation of non-isothermal flow in modular co-rotating twin screw extrusion (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 229-237 
    Details
    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: Non-isothermal flow is simulated in the screw and kneading disc elements in a modular co-rotating twin screw extruder. Methods of calculating mean temperature rises for individual elements are discussed and results are presented. The implications of non-isothermal operation for scale-up is discussed. A method is then described for making calculations in a modular co-rotating machine, that contains many different elements. Example calculations are given showing the tendency of larger machines to buildup greater temperatures when viscous heating is included.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340309
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  • 11
    Electronic Resource
    Electronic Resource
    Influence of a compatibilizing agent on the phase morphology of a polyethylene-polyamide 6 blend in a modular intermeshing co-rotating twin screw extruder (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 221-228 
    Details
    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 of the influence of a compatibilizing agent on phase morphology development in a 75/25 polyethylene/polyamide-6 blend in a modular co-rotating twin screw extruder is presented. The development of phase morphology along the axis of the modular screw was observed by cooling the extruder and removing the polymer from the screw channels. Changes in phase morphology due to the addition of a compatibilizer have been investigated using scanning electron microscopy. Sufficient quantities of compatibilizing agent produce significant increases in the rate of mixing and also reduce the scale of the phase morphology. Much larger quantities (5%) than actually required for interface coverage are needed for rapid mixing. This seems to be due to the high viscosity of the matrix.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340308
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  • 12
    Electronic Resource
    Electronic Resource
    Publications by P. H. Lindenmeyer (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 251-251 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340403
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  • 13
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340401
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  • 14
    Electronic Resource
    Electronic Resource
    Does quantum magic impinge on polymer physics? (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 260-265 
    Details
    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: Penrose states that quantum effects can occur even in relatively large systems when energy differences remain small. This is just the situation with polymer materials. A quantum description by Penrose of the formation of quasi-crystals can be rewritten to apply to polymer crystallization. The implications of the need to take account of quantum effects are discussed. Another approach based on the quantization of energy levels in clusters of atoms offers a possible explanation of heat setting in nylon and polyester fibers. Finally some problems of the interpretation of quantum theory are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340405
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  • 15
    Electronic Resource
    Electronic Resource
    A novel approach to a truly dynamic thermodynamicsEditor's note: Paul Lindenmeyer remained active in his retirement and left a legacy of several manuscripts in various stages of completion. We have selected one of his manuscripts as a contribution to this memorial issue. This paper presents some of the controversial issues of nonequilibrium thermodynamics that Paul was attempting to address. Professor Astarita kindly agreed to provide comments and a critique regarding the approach and ideas advocated by Paul Lindenmeyer. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 252-259 
    Details
    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 novel approach to a truly dynamic thermodynamics is proposed in which equilibrium is defined in terms of explicit time, distance, and acceptable error scales. This approach involves reformulating the second law of thermodynamics in terms of an excess energy that vanishes at equilibrium instead of an entropy that assumes some unknown maximum value. Excess energy is defined mathematically as the total Legendre transform of energy with respect to an independent set of extensive variables. Excess energy is effectively the free energy functional of a nonequilibrium system and is a function of the time, distance, and acceptable error scales. Elimination of entropy from thermodynamics requires recognizing temperature as a thermal stress, proportional to the antimetric component of the stress tensor that is neglected when one assumes the validity of Cauchy's second law of motion. The inclusion of temperature as part of the stress-strain couple completes the science of thermomechanics and opens the way for a practical unification of chemistry and physics in strictly mechanical terms.The last sentence of the abstract shows how high the goals that Lindem meyer set for himself were. I personally do not agree with the idea that mechanics is the queen of all sciences, and that given deep enough probing one could achieve “a practical unification of chemistxy and physics in strictly mechanical terms”; for instance, electromagnetism has full citizenship's rights in physics, and it is hard to conceive that it could be reduced to mechanics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340404
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  • 16
    Electronic Resource
    Electronic Resource
    Characterization of the interfacial bond in paper-polypropylene-paper laminatesDedicated to the memory of Paul H. Lindenmeyer, colleague and friend. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 285-289 
    Details
    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 interfacial strength of two paper-polypropylene-paper laminates used for electrical power transmission cable insulation has been measured using a peel test after a variety of conditionings that simulate the service thermal stress conditions. Immersion in dielectric oil at 23°C causes little decrease in peel strength, but heating in the oil at 90°C causes a rapid initial loss followed by a slow loss of strength. Cyclic and static heating show that cyclic fatigue is not a factor as the initial loss of strength occurs in a time comparable to the first two test cycles and further heating causes much less loss of strength. Tensile and compressive stresses resulting from cable winding have no effect on the loss of bond strength during heating in oil. Vacuum drying of the laminate and oil (as in cable manufacture) before heating results in less decrease in peel strength than heating without prior drying. Optical and electron microscopy show minimal wetting of the paper fibrils by the polypropylene with only a few having been either normal to or at a steep angle to the polypropylene surface. That is, the fibrils appear to be parallel to the interface and only partially immersed in the polypropylene. Micrographs show little, if any, differences between the interfaces on the two sides as well as little paper on the polypropylene after delamination and vice versa. It is suggested that the bonding mechanism is a combination of weak mechanical interlocking and secondary bonds. It is also suggested that swelling of the polypropylene relative to the paper by the dielectric oil at 90°C weakens the interfacial bond.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340409
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  • 17
    Electronic Resource
    Electronic Resource
    The effect of annealing on stretched trans-1,4-polyisoprene networks (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 290-300 
    Details
    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: Variations of stress with temperature for stretched networks of trans-polyisoprene networks in the crystallization region are reported. Such profiles are characteristically U-shaped with the stress at lower temperatures often climbing to high levels. Valley widths of the profiles narrow as annealing temperature increases to about 50°C, then widen at yet higher temperatures. The degree of crystallization at 22°C is 37% and independent of deformation and annealing temperature. The β crystal form is overwhelmingly present with traces of other crystal forms appearing only at high deformations. The theory of stress-induced crystallization provides a good description of experimental results provided the nucleation parameter σ is dependent upon deformation. Therefore, the data provide good qualitative support for the theory in its current form.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340410
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  • 18
    Electronic Resource
    Electronic Resource
    Thermoplastic polyheterocycles. I: Polyalkylene-benzoxazolesPresented in part at the 25th anniversary meeting of the ACS Polymer Group of the North Carolina Section of the American Chemical Society, Chapel Hill, N.C., Nov. 12, 1992. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 301-304 
    Details
    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: Polyalkylenebenzoxazoles of high molecular weight (inherent viscosity values from 0.76 to 2.95) were prepared from 4,6-diaminoresorcinol dihydrochloride and aliphatic diacids in polyphosphoric acid by heating at 180 to 200°C for 3-5 h. Melting points of the polymers ranged from 148 to 423°C, depending on the length of the alkylene chain. Glass transition temperatures were relatively low, ranging from 50 to 100°C and did not show the pronounced odd/even effect noted for melting points. In all cases, rapid weight loss occurred above 400°C. No evidence for the formation of a molecular composite was observed in an attempt to prepare in situ a rod-like polybenzoxazole in a polyalkylenebenzoxazole.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340411
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  • 19
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340201
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  • 20
    Electronic Resource
    Electronic Resource
    Oligomer distribution for interfacial step growth polycondensation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 93-101 
    Details
    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: Low levels of oligomer molecules are generally desirable in polymeric materials. It is known that several reactor variables can affect the oligomer distribution, and therefore it is useful to have predictive models for molecular weight distribution. The normal approach of a differential equation-based model is very complex to set up if it is applied rigorously to include all the non-Flory aspects of the step growth polycondensation and in particular the interfacial polycarbonate polymerization. In this paper, simple methods based on the Monte Carlo method and Stockmayer distribution are applied to simulate the effects of mass-transfer, unequal reactivity, and the starting stoichiometry of the polycondensing functional groups on the oligomer distribution. It is shown that these parameters can have a significant effect on the oligomer weight distribution and polydispersity of the final polymer.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340204
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  • 21
    Electronic Resource
    Electronic Resource
    Mechanical properties and deformation mechanism of polyoxymethylene chain in the crystalline state (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 308-317 
    Details
    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 true crystallite modulus of polyoxymethylene (POM) was evaluated experimentally and thoeretically as a function of temperature. The mechanical deformation mechanism of POM was lattice-dynamically predicted and confirmed by measuring the stress-induced vibrational frequency shifts of the infrared and Raman spectra, which were interpreted on the basis of anharmonic potential field.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340413
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  • 22
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    Analysis of the temperature rise in the projectile and extended chain polyethylene fiber composite armor during ballistic impact and penetration (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 141-152 
    Details
    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 ultra-high strength/modulus, extended chain polyethylene fiber (Spectra® fiber) composite has shown great potential as a lightweight armor material with its extraordinary capability of absorbing the kinetic energy of projectiles. But the relatively low melting point of this fiber (∼ 145°C) has caused concerns regarding the effect of temperature rise during the impact/penetration process on the performance as armor material. In this article, an analysis of temperature rise in projectile and the fiber composite during the impact/penetration process is described. Combining the simulation of impact deformation by finite element analysis and the simulation of temperature rise by a finite difference approximation of the related dynamic equations, the temperature rise caused by the projectile/composite interaction was estimated. Results show that there is a significant temperature rise at the projectile/composite interface due to the friction but that the short length of time involved in the process and the low thermal conductivity of Spectra fiber composite keep the temperature rise in a very small region (in the order of 0.001 cm) around the interface during the impact/penetration process. Consequently, the volume that is affected by the temperature rise is very small, in the order of total 0.001 cm3 around the projectile, and this is too small to generate any detectable effect on the armor performance. After the projectile is stopped, however, substantial heating of fiber composite can occur under specific conditions as the result of heat flow from the hot projectile embedded in the composite. This heating of fibers, however, is a postmortem effect and hence inconsequential to the ballistic performance of the composite armor.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340211
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  • 23
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340301
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  • 24
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    Electronic Resource
    Analysis of a reactor with surface renewal for poly(ethylene terephthalate) synthesis (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 190-200 
    Details
    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 mathematical model of a polycondensation reactor that can be used in the final stage for poly(ethylene terephthalate) (PET) is established and compared with experimental data obtained from a laboratory scale reactor with film renewal. Detailed side reactions are considered along with the diffusional removal of the small molecules through thin film. Among several kinetic constants, the polycondensation reaction rate constant k1(= k8) and diester group degradation reaction rate constant k7 have an influence over the degree of polymerization. The values of k1(= k8) and k7 for 0.05 wt% Sb2O3 were obtained as curve-fit values: (1) k1(= k8) = 3.4 × 106 exp(- 18.500/RT′) (L/mol-min); (2) k7 = 1.3 × 1011 exp(- 37,800/RT′) (min-1). Effects of the film exposure time, reduced pressure of vacuum, temperature, the initial terephthalic acid (TPA)/ethylene glycol (EG) mole ratio, the initial degree of polymerization, and catalysts were well explained by the model.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340304
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  • 25
    Electronic Resource
    Electronic Resource
    Entrance effects for power-law fluid (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 209-212 
    Details
    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: Entrance pressure losses for the creeping flow of a power-law fluid are calculated for an abrupt contraction of ratio 2, 4, 8 and ∞ for both the axisymmetric and planar cases using P2P1 and P+2P1 finite elements. Contrary to some earlier findings in the literature, the entrance pressure loss obtained by using the two different types of finite elements, both of which satisfy the Babus̆ka-Brezzi condition, are found to converge to the same results. The present results also confirm that the variational method of Duda and Vrentas gives excellent upper bounds for both the axisymmetric and planar cases with infinite contraction ratio.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340306
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  • 26
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    Semianalytical solution for epoxy-amine curing in the presence of nonisothermal effects (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 405-413 
    Details
    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 curing of epoxy-amine polymer has been modeled by the reaction of functional groups, and the mole balance of these is governed by a set of six nonlinear differential equations. In this work, we have first developed a complete analytical solution for isothermal curing. For nonisothermal curing, we have divided the domain of hydroxyl group concentration β into small increments Δβ and adopted our analytical results for this domain. In addition, we solved the energy balance equation analytically and obtained the temperature rise for Δβ. We have compared our results with those obtained from the Runge Kutta numerical solutions. We have shown that our semianalytical technique is about a thousand times more efficient and faster.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340505
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  • 27
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    Electronic Resource
    Shear test for thermoplastic polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 513-518 
    Details
    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 shear test is proposed as a complement to the tensile test in order to characterize the short time mechanical behavior of thermoplastic polymers. The proposed test geometry makes the test easy to perform and to evaluate and gives relevant information about anisotropy, plastic deformation, crack initiation, and propagation properties. Three different materials have been tested and the results are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340609
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  • 28
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    Residual stress development in neat poly(etheretherketone) (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 500-506 
    Details
    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: Material property models for poly(etheretherketone) (PEEK) have been combined with a residual stress model to provide a means for investigating the effect of crystallization process on the residual stress development in semicrystalline materials. The analysis shows that crystallization causes an increase in the residual stress levels. This increase is affected through an increase in the resin modulus values and through the resin modulus build-up at higher temperatures. The shrinkage due to crystallization was found to have no effect on the residual stress development in neat PEEK.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340607
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  • 29
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    Viscoelastic properties of a 60 mol% para-hydroxybenzoic acid/40 mol% poly(ethylene terephthalate) liquid crystalline copolyester. II: Effect of shear historyPart of this work was originally presented at the International Regional Meeting of the Polymer Processing Society in Seoul, Korea, September 26-29, 1990. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 519-527 
    Details
    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: Temperature sweeps of dynamic viscoelastic properties have shown that phydroxybenzoic acid (PHB)-based liquid crystalline polyesters, specifically in this case those copolymerized with poly(ethylene terephthalate) (PET), can be subjected to considerable supercooling if initial heating curves are compared to subsequent cooling curves, indicating that this type of material can be in quite different states even at the same temperature, depending on thermal history. Utilizing this supercooling behavior, viscoelastic properties of a 60 mol% PHB/40 mol% PET material produced by Unitika were monitored before and, particularly, after large-scale shear deformation to determine how potential structure changes induced by the shear are reflected in viscoelastic properties immediately, and with time. According to dynamic viscoelastic temperature sweep data four quite different initial states were employed including conditions with, as well as largely free of, crystallites. However, in all cases, post-shear monitoring showed decreased G′ and G″ values with almost no evidence of return towards initial values within approximately 25 min. These results, in addition to furthering somewhat the fundamental understanding of the flow and relaxation properties of liquid crystalline polymers, may be useful in polymer processing, where large-scale shear deformations employed in forming processes appear to be capable of changing considerably the subsequent behavior of such materials.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340610
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  • 30
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    Correlation for volume phase transition of polymeric gel (vinyl alcohol-sodium acrylate copolymer) in alcohol-water solutions (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 507-512 
    Details
    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 thermodynamic model was proposed to correlate the phase behavior of a swelling polymeric gel (vinyl alcohol-sodium acrylate copolymer) and the volume phase transition in alcohol (methanol, ethanol or propanol)-water solutions. The model is based on the Flory-Huggins formula for polymer solution coupled with the osmotic pressure by rubber elasticity proposed by Flory. The volume change behavior and the equilibrium concentrations inside and outside the gel were successfully correlated using the present model.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340608
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  • 31
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    Radical terpolymerization of zincacrylate, acrylonitrile, and styrene initiated by As2S3-styrene complex (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 528-531 
    Details
    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: Terpolymerization was investigated by dilatometry for zincacrylate (ZnA2), acrylonitrile (AN), and styrene (St), radically initiated by a As2S3-styrene complex (I) in dimethyl sulphoxide (DMSO), at 90 ± 0.1°C for 1 h under inert atmosphere. The system follows non-ideal kinetics, due to primary radical termination as well as a degradative chain transfer reaction. The kinetic expression for the system is Rpα(I)0.27 (St)0.31 (AN) 0.22[ZnA2]0.12. The value for the activation energy and kp2/kt are 55 kJ mol-1 and 1.87 × 10-7 1 mol-1 s-1 respectively. The terpolymer has been characterized by IR and NMR spectroscopy. The thermal stability and solubility of the terpolymer have also been studied.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340611
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  • 32
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340701
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  • 33
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    Flow field analysis of an intermeshing counterrotating twin screw extruder (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 551-558 
    Details
    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 intermeshing counterrotating twin screw extruder is widely used for compounding, devolatilization, blending, and reactive extrusion. A fluid dynamics analysis package-FIDAP, using the finite element method, was implemented to simulate the 3-D flow patterns in the region of conveying elements and shearing discs of a Leistritz LSM30.34 twin screw extruder. The rheological behavior of the fluid was described by a power law model. The flow fields were characterized in terms of velocity profiles, pressure distributions, shear stresses generated, and a parameter λ quantifying the elongational flow components. The influence of screw rotational speed and axial pressure difference on the flow characteristics was also analyzed. A comparison between the flow characteristics in the shearing discs operated in a corotating or counterrotating mode was also presented.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340703
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  • 34
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    Heterogeneous suspension polymerization of vinyl chloride: Phase distribution and evolution (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 532-540 
    Details
    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 model for the phase distribution and evolution of the heterogeneous (suspension) polymerization of vinyl chloride is presented. Experimental information on pressure, temperature, and conversion has been obtained from a 34 liter bench reactor reproducing reaction conditions and product properties typical of industrial operation. A calculation procedure based on simple plant data is proposed for the description of the phase compositions and their evolution over the entire process. Results based on classical Flory-Huggins theory of solutions are presented and compared with existing data.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340612
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  • 35
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    Multilayer extrusion: Experiments and computer simulation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 559-569 
    Details
    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 mathematical model is presented for the computer simulation of multilayer flow of polymer melts in coexitrusion. The proposed model can handle an arbitrary number of layers. The viscosity of each layer is shear-rate and temperature dependent. Given the material properties, die dimensions, and process conditions, the model determines the flow field throughout the die gap. Computer simulations and experimental data are presented for a three-layer polyester/EVA/polyester film coextrusion, with emphasis on the interfacial instability and its effects on optical properties of the film. The rsults are discussed in the context of the critical interfacial shear stress criterion that has been proposed by Schrenk, et al. (1) for the onset of interfacial instability. It appears that elasticity differences between layers contribute to the interfacial instability. It is conjectured that minimizing interfacial shear stress and matching elasticities of adjacent layers is an appropriate criterion in coextrusion analysis.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340704
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  • 36
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    A unified lubrication approach for the design of a coat-hanger die (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 541-550 
    Details
    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 simple unified lubrication approach has been proposed to design a coat-hanger die that can deliver wide and uniform liquid sheets. This approach requires that the wall stress in the manifold be constant. With this constraint, any inelastic non-Newtonian fluid model can be used to describe the liquid motion inside the die. Fluid models that can represent the pseudoplastic or viscoplastic behavior of polymeric liquids have been selected for illustration. A general equation that can be solved to determine the effect of production variations on flow uniformity inside the die has also been derived.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340702
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  • 37
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    Electronic Resource
    Mechanism of shear modification of low density polyethylene (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 570-579 
    Details
    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 this paper we address the aspects associated with shear modification of low density polyethylene by extrusion. By successive passes of the polymer through an extruder it can be shown that both the melt viscosity and melt elasticity are reduced by shear modification. These reversible variations are not accompanied by significant changes in molecular weight distribution. The major effects of extrusion are to decrease the amount of elastically effecitve material. Study of proton relaxation times at 150°C shows that the melt comprises regions of relatively ordered, entangled, and unentangled polymer. Shearing reduces the proportion of more ordered material. The elastically effective anchors that are reduced by shearing are regions with restricted segmental mobility rather than conventional entanglements or intermolecular knots. Successive extrusions produce a relatively small decrease in the number of such constraints to molecular motion. Repeated shearing has a diminishing effect on the proportion of more ordered material in the polyethlene melt. This parallels observations of the effects of repeated shear modification on the properties of polyethylene films and other extrudates.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340705
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  • 38
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    Controller design and performance analysis for a reactive extrusion process (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 585-597 
    Details
    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 paper presents the design and analysis of a process control strategy for a reactive extrusion polypropylene degradation process. The primary control objective is to continuously produce polypropylene with desired properties (viscosity) despite variations in the properties of the feed material. The viscosity of the polypropylene, measured using an In-line Wedge Rheometer, is controlled by manipulating the feed concentration of the peroxide which acts as the initiator for the degradation reaction. An empirical model of the reactive degradation process is developed which describes the process dynamics and the characteristic process disturbances. Minimum variance (MV), constrained minimum variance (CMV), and pole placement (PP) controllers are first evaluated and compared in simulation. Then, a pole placement controller is implemented on the actual reactive extrusion process, with results being presented for the response of the controlled process to load disturbances due to feed material changes.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340707
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  • 39
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760340801
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  • 40
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    A sliding plate normal thrust rheometer for molten plastics (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 580-584 
    Details
    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 sliding plate rheometer has been developed to measure the normal thrust of a molten plastic in large amplitude oscillatory shear. The normal thrust of a molten plastic in large amplitude oscillatory shear is a significant nonlinear effect that has previously been unobtainable. Normal thrust measurements may now be used to help understand and characterize nonlinear viscoelastic behavior inherent in most molten plastics. The new rhemoeter incorporates a piezoelectric pressure transducer in a very stiff plate that minimizes compliance. Normal thrust measurements with cone and plate rheometers are made by measuring the total force on the plate (or cone) and are subject to error due to edge effects. The new rheometer measures the local pressure in the sample and is therefore unaffected by sample size or edge effects. Normal thrust measurements in large amplitude oscillatory shear are reported for both molten Phillips TR480 high density polyethylene pipe resin which contains 2% by weight of carbon black filler and IUPAC LDPE X. Crosstalk due to shear stress on the active face of the pressure transducer causes signal error which for oscillatory shear is filtered out using a discrete Fourier transform.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340706
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  • 41
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    Influence of a core/shell rubber phase on the morphology and the impact resistance of a PC/SAN blend (75/25) (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 613-624 
    Details
    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: At 75/25 concentration ratio, bisphenol a polycarbonate (PC)/styreneacry-lonitrile copolymer (SAN) blend has poor impact resistance compared to PC/ABS. A rubber phase methacrylate-butadiene-styrene (MBS) of core/shell type was dispersed in PC/SAN blend. The morphology of the unmodified and modified blend was investigated. The influence of the acrylonitrile ratio in the SAN on the microstructure was studied. It clearly shows that core/shell resides at the interface between PC and SAN. It seems that core/shell particles enhance the adhesion between the different phases. Their presence influences the interface mobility; i.e., the coalescence of the dispersed phase observed in pure PC/SAN is considerably reduced when the MBS particles are added. The impact resistance of the samples was correlated with the morphology.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340802
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  • 42
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    Modeling of polypropylene degradation during reactive extrusion with implications for process control (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 598-612 
    Details
    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 paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340708
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  • 43
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    Rubber modified epoxy resin. I: Cure kinetics and chemorheology (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 625-631 
    Details
    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 curing and vitrification effect during the reaction of ATBN modified epoxy resin was studied through the dynamic differential scanning calorimetry method and a new reaction kinetic equation containing generalized WLF equation was developed to describe the reaction rate at both glassy and rubbery state. An autocatalytic mechanism was found to describe adequately the cure kinetics of the rubber modified epoxy resin and the overall order of reaction was assumed to be 2. The kinetic parameters were determined from the DSC data through the Marquardt's multivariable nonlinear regression method and Runge-Kutta integration technique. The presence of rubber indicated minor effect on the cure kinetics of epoxy resin. The Arrhenius type viscosity function was employed to establish a relationship between viscosity data measured by RMS and chemical conversion calculated from the reaction kinetic equation.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340803
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  • 44
    Electronic Resource
    Electronic Resource
    Modeling of the Dynamics of Water and R-11 blown polyurethane foam formation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 642-649 
    Details
    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: Polyurethane foam formation involves both polymerization and expansion processes. The dynamics of the water and R-11 blown foams depend on the rates of chemical and physical blowing processes, along with the rate of viscosity increase of the reacting mixture. Experiments were carried out to study the dynamics of free rising, water and R-11 blown rigid polyurethane foams. The density and temperature change during the foam formation were monitored. A theoretical model was developed to predict the density and temperature variation with time. In the model, the physical blowing agent (R-11) evaporation process is assumed to be heat generation-controlled and the carbon dioxide generation process to be controlled by the rate of the water-isocyanate reaction. The kinetic parameters of the reactions of isocyanate with polyol and water were obtained separately and were asssumed to be independent of each other. The water-isocyanate reaction appears to follow first-order kinetics with respect to concentration of water. The theoretical predictions of the model show good agreement with the experimental data for density variation with time. The model predictions for temperature rise also match experimental data, except at the later stages of foaming when it is found to be slower than the experimental measurements. However, this deviation does not affect the dynamics of density change since it occurs after the completion of the expansion process.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340805
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  • 45
    Electronic Resource
    Electronic Resource
    A personal computer software program for coathanger die simulation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 657-664 
    Details
    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 good extrusion die must distribute the polymer melt in the flow channel such that the material exits from the die with a uniform velocity and temperature. Coathanger dies are commonly used for the extrusion of plastic sheets and films. The die is usually provided with a straining bar allowing a regulation of the flowrate in the case of a poor design. But this, in turn, can affect temperature uniformity. Therefore, the design of coathanger die is a complex task which is mainly accomplished by trial and error in industry. Analyses of the flow in coathanger dies have been reported in the literature. Analytical and numerical approaches are used to solve this problem. The first one involves many simplifying assumptions: the most important ones being the unidirectional and isothermal flow of the polymer. Most numerical methods deal with a 2-D geometry, but only a few of them have considered the non-isothermal flow. A new model has been developed using a modified FAN method (Flow Analysis Network introduced by Tadmor) for the calculation of the 2-D flow, coupled with a finite-difference scheme for the calculation of temperature. The overall model can run on a PC with only a few minutes of calculation. Good agreement was obtained between experimental data and simulations.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340807
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  • 46
    Electronic Resource
    Electronic Resource
    A finite element model for complex profile calibration (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 650-656 
    Details
    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 finite element model named Corrected Slice Method (CSM) has been developed to cope with three-dimensional vacuum cooling calibrator problems. Such problems appear whenever the cooling channel lay-out comprises transverse channels in the calibrator. The CSM is an extension of the 2D approach (8), which takes into account the axial heat fluxes within the calibrator. The proposed model was validated by comparing the numerical results obtained on a test problem with a rigorous finite element approach. Moreover, a real complex profile-calibrator system was simulated in order to illustrate the full performance of the porposed method.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340806
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  • 47
    Electronic Resource
    Electronic Resource
    The use of flexural tests in the study of environmental stress cracking of polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 665-670 
    Details
    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 use of bend testers for the determination of critical strains in the study of environmental stress cracking has been assessed. Using the combination of polystyrene in ethanol, various factors affecting the measurement of critical strains were investigated, including the strain applied during the bend testing, the time of immersion in the liquid prior to straining, the surface finish, and the extent of physical aging. It was concluded that the best determination of critical strain is the strain at which a sample just shows signs of crazing, rather than the strain at the outer edge of a band of crazes. The measured value of critical strain increases with increased prior immersion time, decreased surface roughness, and decreased physical aging time. Reasons for these variations are discussed. It is concluded that although the use of bend testers is valuable for qualitative testing, careful testing methodologies need to be adopted for it to be a useful quantitative test.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340808
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  • 48
    Electronic Resource
    Electronic Resource
    Modeling of the dynamics of R-11 blown polyurethane foam formation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 632-641 
    Details
    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 dynamics of R-11 blown polyurethane foam formation depend on the rates of viscosity increase of the reacting mixture and R-11 evaporation, and both are controlled by the polymerization process. Detailed experiments were carried out to study the dynamics of foaming and the measurements made included the cream and rise times, the density change of the expanding foam with time, and the temperature rise during reaction. Dynamic temperature measurements at different points in the foaming mixture were also made to study the spatial variation of the temperature in the foam. The experimental results showed the rate of foaming, the final density, and the maximum temperature decreased with increasing R-11 concentration. The heat losses from the foam were also found to be significant towards the later stages of foaming when density was low. Theoretical models were developed to predict the temperature and density change with time and spatial variation of temperature in the foam due to heat losses, by considering the foaming dynamics to be either heat generation controlled or heat and mass transfer controlled. In the former, the foam was assumed to be a pseudohomogeneous phase and the approach was similar to that of Rojas, et al. (5). New features accounted for in the model were dilution of the reactant concentration due to the presence of liquid blowing agent and heat loss from the foam due to radiation. While excellent agreement between theoretical predictions and experimental results was obtained for temperature variation with time at different locations in the foam, the model gave a much sharper reduction in density with time as compared to the experimental data. In the second model, the rate of foaming was assumed to be controlled by the rate of heat and mass transfer to a single bubble in the foam. Assuming a film model for heat and mass transfer, the theoretical predictions for both temperature and density were found to be in very good agreement with experimental data.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340804
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  • 49
    Electronic Resource
    Electronic Resource
    Masked edge effects when measuring diffusion coefficients with the cup method (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 821-826 
    Details
    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: When diffusion coefficients are measured with the cup method, the exposed area is often less than the area of the sample. Because of this masking effect the measured diffusion coefficient is overestimated. The present article presents simple formulas based on two-dimensional analytical solutions to correct for this in cylindrical cup samples. Different cases of anisotropical diffusion are dealt with. The error in the analytical solutions is determined by numerical computer simulations.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341007
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  • 50
    Electronic Resource
    Electronic Resource
    Comparative study of warpage, global shrinkage, residual stresses, and mechanical behavior of rotationally molded parts produced from different polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 815-820 
    Details
    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 comparative study of warpage, global shrinkage, and residual quench stresses developed in rotational molding is made for a series of thermoplastics including various polythylenes, polypropylene, polyamide-6, polycarbonate, and polystyrene. The influence of rate of quench on uniaxial stress strain and impact behavior of rotomolded parts was also studied. Generally, warpage, global shrinkage, and residual stresses increase with increasing quench rate for all the polymers. Further, the levels of warpage and global shrinkage increases with extent of crystallization, i.e., products from glassy polymers exhibit little warpage and those from highly crystalline polymers are highly warped. Increasing rate of quench tends to increase elongation to break and impact strength.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341006
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  • 51
    Electronic Resource
    Electronic Resource
    Nonisothermal elongational behavior of blends with liquid crystalline polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 799-803 
    Details
    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: Measurements of melt strength and breaking stretching ratio of several blends of thermoplastic polymers with liquid crystalline polymers are presented. The melt strength behavior depends not only on the viscosity of the blends but also on the temperature dependence of the viscosity. In particular, even if the viscosities of the blends are, at the extrusion temperature, lower than that of the thermoplastic matrices, the melt strength can be larger than that of the pure thermoplastics if its viscosity-temperature curve exceeds that of the matrices far from the solidification temperature. This behavior allows one to spin or film blow these blends despite the low viscosity.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341004
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  • 52
    Electronic Resource
    Electronic Resource
    High pressure polymerization of ethylene and rheological behavior of polyethylene product (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 804-814 
    Details
    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 mathematical model of the high pressure polymerization of ethylene in tubular reactors was tested with experimental data obtained from an industrial size tubular reactor. Series of experiments involving changes in operating conditions were carried out, and process data and polyethylene samples were collected. The collected samples were characterized for their molecular weight distributions and various rheological material functions involving shear and extensional flows. The findings of the model were compared against the generated process data and the molecular weight distributions of the samples. The determined rheological behavior exhibited strong dependence on the primary characteristics of the resins. Overall, this study should introduce a better understanding of the interactions between high pressure reaction conditions and the primary properties of polyethylene, including moments of molecular weight distribution and extent of branching on one hand and the interrelationships between primary properties and the rheological behavior of the high pressure polyethylene product on the other hand.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341005
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  • 53
    Electronic Resource
    Electronic Resource
    Three-dimensional finite element analysis of polymeric fluid flow in an extrusion die. Part I: Entrance effect (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 827-834 
    Details
    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 Galerkin finite element method has been applied to study the three-dimensional flow field of power-law fluids inside an extrusion die. Two inlet designs, i.e., center-fed and end-fed, have been considered. The effects of inertial force as represented by the Reynolds number Re, inlet geometry, and the power-law index n on lateral flow uniformity and vortex formation in the entrance region have been examined. A flow visualization technique has been carried out to experimentally verify the theoretical prediction of the three-dimensional flow field inside a die. It has been found that increasing Re or decreasing n will deteriorate flow uniformity. Depending on the direction of the inlet jet stream, the inertial force may create a flow peak in the central region of a center-fed die, or the maximum flow rate will appear close to the end of the die for an end-fed die. For highly shear-thinning fluids, lower flow rates are always observed close to the end of the dies. It is concluded that creating a plug flow in the inlet tube of the extrusion die is advantageous for both center-fed and end-fed designs.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341008
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  • 54
    Electronic Resource
    Electronic Resource
    Numerical simulation of the post-filling stage in injection molding with a two-phase model (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 835-846 
    Details
    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 two-phase model is presented for simulating the post-filling stage of injection molding of amorphous and semicrystalline materials. A finite-element scheme with quadratic shape function for the pressure is proposed. The melt is considered in terms of Hele-Shaw flow for a non-Newtonian fluid using a modified-Cross model with either an Arrhenius-type or WLF-type functional form to describe the viscosity under nonisothermal conditions; the compressible behavior of the polymer is assumed to obey either a double-domain Tait or single-domain Spencer Gilmore equation of state. The interfacial energy balance equation including the latent-heat effect for semicrystalline materials is coupled with the transient energy equation for the solid and melt phases in order to predict the solidified layer and temperature profile. Two well-characterized materials, namely a commercial-grade PP and PS, were used in the present work. Good agreement is obtained between the present simulation and experimental pressure traces from this study and from previous investigation in the literature. The effects of compressibility, viscosity model, and thermal properties upon the predicted pressure field are also considered.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341009
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  • 55
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760341101
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  • 56
    Electronic Resource
    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760341501
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  • 57
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    Electronic Resource
    Generation of microcellular polymeric foams using supercritical carbon dioxide. II: Cell growth and skin formation (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1148-1156 
    Details
    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: We have generated microcellular polymeric foam structures using a pressure induced phase separation in concentrated mixtures of supercritical CO2 and poly(methyl methacrylate). The process typically generates a microcellular core structure encased by a nonporous skin, the thickness of which decreases with increasing saturation pressure. This trend can be described by a model for skin formation that is based on the diffusion rate of gas out of the sample. Significant density reductions on the order of 30 to 70% can be achieved by changing the pressure and temperature conditions in the foaming process. There are several ways in which the saturation pressure affects the average cell size, with the net effect that cell size decreases sharply with increasing pressure above 2000 psi, leveling out at higher pressures. Cell size increases with increasing temperature from 40°C to 70°C. A model for cell growth, based on a cell model of Aremanesh and Advani, modified to include the effect of CO2 on model parameters, reproduces these trends.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341408
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  • 58
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    Electronic Resource
    Multiobjective dynamic optimization of a nonvaporizing nylon 6 batch reactor (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1161-1172 
    Details
    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: Multiobjective dynamic optimization has been carried out on a nonvaporizing nylon 6 batch reactor. Three objective functions have been identified, viz., minimization of the concentration of unreacted monomer in the product, minimization of the dimer concentration, and minimization of the reaction time, for producing polymer having a specified value, μn, d, of the number average chain length. Two problems have been studied in this paper, each consisting of two objective functions taken from the above set. Pareto solutions have been generated using an algorithm based on Pontryagin's minimum principle and the method of Lagrangian multipliers. The effects of various physical and computational parameters have been studied, and methods have been developed to overcome the numerical difficulties that arise during the solution. The Pareto sets so generated can be coupled with the surrogate worth trade-off (SWT) method, which facilitates interaction with a decision maker (DM). The optimal temperature histories obtained for the two problems studied are quite different and suggest that one must solve the three-dimensional problem in which the vector objective function incorporates all three objective functions. Results from the present study could be used as starting guesses to converge rapidly on the solution of the three-dimensional problem.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341502
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  • 59
    Electronic Resource
    Electronic Resource
    Entrance pressure drop studies of corn meal dough during extrusion cooking (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1187-1195 
    Details
    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 entrance pressure drop during extrusion cooking of corn grits was measured using a cylindrical die viscometer attached to a single screw extruder and compared with results obtained using low-density polyethylene (LDPE). The cylindrical die viscometer had a length to diameter ratio of 40 with half-entry angles of 30, 37.5, 45 and 90° with the horizontal. The entrance pressure drop at the die was measured as a function of extrusion temperature, product moisture content and the die entry angle. Results indicate that the flow behavior of corn grits and the entrance pressure drop were affected by product moisture content, process temperature and the shear history in the extruder. Entrance pressure drop also increased with wall shear stress for plastic melt, but for food biopolymer, the increase was observed provided shear history effects were minimized. Entrance correction increased with apparent shear rate for LDPE, but the reverse was true for corn meal. Using Cogswell's analysis, corn grits exhibit severe extension thinning behavior in entry flow.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341504
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  • 60
    Electronic Resource
    Electronic Resource
    Isocyanate trimerization kinetics and heat transfer in structural reaction injection moldingBased on work presented at the Advanced Composites Conference, Detroit, October 1991. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1173-1186 
    Details
    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: Guidelines are developed for molding large composite parts via structural reaction injection molding using glass preforms and polyisocyanurate resins. These are based on numerical simulations of the simultaneous heat transfer and reaction kinetics of a commercial system during and after mold filling. Premised requirements are that resin does not gel before the mold is filled, yet, reactions are sufficiently vigorous to approach completion. An existing mechanistic kinetic model is used and material parameters found from a chemical kinetics study employing an insulated cup. It is found desirable to use a high mold temperature and a low preform temperature in molding. Nondimensionalization of the governing equations reveals the existence of a Nusselt number (Nu), which describes the relative importance of heat transfer between resin and glass relative to thermal diffusion to the mold wall. With a Nusselt number of about 50 or higher it is possible to use the cooling capacity of the preform to extend gel time. The magnitude of Nu is influenced by part thickness, glass fraction, strand diameter, and flow velocity. Thus, the effect of the preform on extending resin gel time is within control of the molder.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341503
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  • 61
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    A study of the effect of the extrusion variables and screw design on the thermal and rheological characteristics of acetal and nylon 66 (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1196-1201 
    Details
    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 detailed study of the effect of several extrusion variables was made on the rheological and thermal properties of Delrin II acetal homopolymer and Zytel 42 polyamide 66 materials. A 63.5 mm Davis Standard extruder was used to measure the effect of screw design, screw rpm, die and head pressure, and melt temperature on the rheology of acetal and nylon 66 resins. A single stage metering screw was used to determine the effect of screw geometry and viscous heating on the melt viscosity breakdown and the rate of degradation of each polymer. The melt temperature was measured in the melt stream in the channel and correlations are shown between ideal melt temperature predicted from the rheology data and the actual loss of properties of each polymer due to viscous heating. The paper also discusses how to measure the melt temperature accurately in extrusion, and to use it as a key indicator to optimize the extrusion process, and to control the rheology, thermal stability, and the molecular weight of a polymer during processing.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341505
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  • 62
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    Weld lines and mechanical properties of injection molded polyethylene/polystyrene/copolymer blends (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1202-1210 
    Details
    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 this article, we investigate the effect of weld lines on the tensile mechanical properties of unmodified and copolymer modified high density polyethylene (HDPE) and polystyrene (PS) blends. The homopolymers were melt blended in the proportion of 20 wt% HDPE and 80 wt% PS using a twin screw extruder at a temperature of 200°C. The results show that the mechanical properties are generally lower when weld lines are present. The decrease of the mechanical properties is much more pronounced for the blends. The addition of small amounts of a commercial styrene/butadiene copolymer significantly improves the strength and the elongation at break of this blend. An optimum copolymer concentration was observed at 3 wt%. This value coincides with the interphase saturation concentration of the copolymer obtained from the analysis of the DMTA (dynamic mechanical and thermal) properties of the blends. The copolymer was also found to induce important changes in the morphology of the blend. The interdiffusion of the polymer fronts in the weld region was also improved by the presence of the copolymer. It is believed that these two aspects contribute to the enhanced properties obtained with copolymer modified blends in presence of weld lines. An important effect of the injection temperature on the tensile strength and the elongation at break of welded samples with copolymer modified blends was observed. The effect of mold temperature on these properties was less important mainly at low injection temperatures. Only a slight effect of these two parameters was observed for the tensile modulus in the range of mold and injection temperatures considered in this study.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341506
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    Experimental study of transcription of minute width grooves in injection molding (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1211-1218 
    Details
    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 injection molding of substrates for optical discs, precise transcription of pits and grooves is very important. For high-density optical discs, molding transcription for minute grooves with widths on the sub-micron level is required. In this paper, in order to clarify the relationship between molding conditions and transcription quantitatively, transcription of minute rectangular grooves (width 0.55 μm, depth 70 nm) in injection molding of polycarbonate resin was studied. The relationship between molding conditions and the transcription heights was verified. And, by introducing the equivalent thickness of the vitrified layer concept, a transcription model related to the minute groove width is proposed. This equivalent thickness of the vitrified layer is estimated to be 100 to 150 nm at the point of filling completion under a certain molding condition. Also, using the above description of the equivalent thickness of the vitrified layer, it is possible to estimate the extent of transcription under the various molding conditions.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341507
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    Electronic Resource
    Masthead (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    Details
    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
    URL: http://dx.doi.org/10.1002/pen.760341601
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  • 65
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    Flow field analysis of a cavity transfer mixer (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1224-1230 
    Details
    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 cavity transfer mixer (CTM) was primarily designed as a distributive mixing device to be used as an add-on unit to existing extruders. In determining the CTM overall mixing efficiency as well as its potential use for various applications, the flow patterns/characteristics within this mixer must be well understood. In this work, a fluid dynamics analysis package, FIDAP, based on the finite element method was employed to simulate the flow patterns in a CTM with 6 rows and 4 cavities per row. A 3D, isothermal flow analysis was carried out and the fluid of choice was a flexible polyvinylchloride whose rheological behavior is described by a power-law model fluid. The flow field was characterized in terms of velocity profiles, pressure distributions, shear rates/shear stresses generated and a parameter λ quantifying the elongational flow components. The results of the flow simulations were compared with experimental data. The CTM potential use for dispersive mixing was discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341509
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  • 66
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    Moldability studies for the reaction injection molding of polydicyclopentadiene (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 929-936 
    Details
    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: Moldability diagrams for the filling and curing stages of a dicyclopentadiene (DCPD) based reaction injection molding (RIM) system were established based on a simplified engineering approach. Initial monomer temperature and filling time are the critical parameters for the filling stage whereas in the curing stage, mold wall temperature and demold time proved to be the main processing variables. The physical and thermal properties of the molded samples were examined and the results indicate that such simplified moldability diagrams are sufficiently accurate to establish the processing conditions for the system under investigation.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341110
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  • 67
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    Anisotropy in injection-molded ethylene-propylene-diene rubbers. Part II: Disks delaminated by a water-jet cutting technique (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 913-920 
    Details
    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: Anisotropy and molecular orientation are well known phenomena in the field of thermoplastics, but only a few studies have described anisotropy in rubber materials. It has been shown that injection molding gives rise to a higher degree of anisotropy than compression molding. The anisotropy in the rubber material was strengthened by carbon black and is presumably due to molecular orientation. This paper describes the anisotropy of injection-molded ethylene-propylene-diene rubbers. The two polymers had different molecular weight distributions and thus different rheological properties. The compounds were injected into center-gated 4mm thick disks. The disks were subsequently split into three layers using a water-jet cutting technique. Measurement of mechanical and swelling properties in the different layers and directions showed that the anisotropy varied through the thickness of the disk. By X-ray scattering it was shown that rubber molecules had a preferred direction and thus, that the anisotropy was probably predominantly due to molecular orientation created during the mold filling.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341108
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  • 68
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    Air drag on fine filaments at oblique and normal angles to the air stream (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 958-964 
    Details
    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: Measurements are reported for air drag on fine filaments whose axes are oriented at oblique and normal angles to the air velocity. In terms of the drag coefficient CDN the data are fit well by the following relation: CDN = 6.96(ReDN)-0.440(d/d0)0.404, where ReDN is the Reynolds number based on flow normal to the fiber axis, and d/d0 is a dimensionless fiber diameter. A wide range of conditions were tested: filament diameters ranged from 13 to 390 microns, gas velocities ranged from 22 to 83 m/s, and fiber Reynolds numbers ranged from 29 to 2120.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341203
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    Some effects of irradiation on properties of filled PVC compounds (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 981-985 
    Details
    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: Compounds based on poly(vinyl chloride) (PVC), and containing CaCO3 filler and trifunctional acrylic crosslinking agent have been crosslinked by exposure to γ-rays at dosages to 70 kGy. The crosslinking agent was found to be essential for crosslinking to proceed, only minor sensitivity to the irradiation having been found in compounds omitting the chemical. The presence of filler somewhat inhibits crosslink effectiveness, as measured by solvent uptake data. Elastic moduli and elongations at rupture respond to crosslinking processes, the latter being particularly sensitive to the effects of irradiation. The presence of filler was found to raise modulus, while ductilities of compounds were greater than expected, owing to adhesion at polymer/filler interfaces. Favorable acid/base interaction forces appear responsible for the effect. The reduced sensitivity of filled PVC compounds to γ-ray exposure is attributed to polymer immobilization, the consequence of strong interfacial bonding with the filler.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341206
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  • 70
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    Spinnability of ultrasonically synthesized poly(vinyl alcohol-b-acrylonitrile) emulsions (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 975-980 
    Details
    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 relationship between spinnability and composition of poly(vinyl alcohol)/polyacrylonitrile block copolymer emulsions prepared by an ultrasonic technique is presented. Theoretical analysis and experimental investigation by multiple techniques show that the micellar structure characteristics of the block copolymer emulsions and the behavior of emulsion in shear flowing and coagulating in spinning process are the key factors affecting the spinnability. The mechanical properties of the final fibers are related to the composition, molecular weight, spinnability of the copolymers, and the processability of the as-spun fibers.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341205
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  • 71
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    Non-Newtonian and isothermal analysis of flow of poly(methyl methacrylate) in a model twin screw extruder. Part I (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 986-994 
    Details
    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 flow analysis network (FAN) method was modified to analyze the flow of poly(methyl methacrylate) (PMMA) in a model counter-rotating nonintermeshing screw extruder. The numerical prediction of the pressure profiles was compared with the experimental results. Flow patterns in the screw elements of the model counter-rotating nonintermeshing twin screw extruder were also predicted. A new flow path method was developed to calculate the residence time distribution. This result will be applied to analyze the flow during the reaction in the model twin screw extruder.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341207
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  • 72
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    Toward a high-impact isotactic polystyrene (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1005-1010 
    Details
    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: Brittle isotactic polystyrene has been toughened by the presence of emulsified rubber particles. Semicrystalline diblock copolymers of isotactic polystyrene and polybutadiene functioned successfully as emulsifying agents, as revealed by the results of scanning and transmission electron microscopy. Semiquantitative measures of the toughness of the various materials were obtained via a home-built micromechanical testing device. The minimum amount of copolymer required to achieve emulsified morphologies and significant toughness depended on the thermal history of the material being tested.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341209
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  • 73
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    Viscoelastic-plastic deformation behavior of polypropylene after cyclic preloadings (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1319-1326 
    Details
    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: Stress-relaxation behavior is studied in polypropylene samples subjected to different cyclic preloadings and to simple tension. The relaxation tests are performed under different sets of strain amplitude, number of cycles, and strain rate, using a closed-loop, electrohydraulic, servocontrolled testing machine. The calculated stress-strain curves are determined from a constitutive equation based on an overstress theory in which an equilibrium stress and a viscosity function are treated. The calculated results agree well with the experimental ones. It is concluded that the overstress theory explains the nonlinear viscoelastic-plastic behavior of polypropylene.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341704
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    Zone drawn NEW-TPI thermoplastic polyimide and its blends with Xydar liquid crystalline polymerBased on presentations made at the American Chemical Society Meeting, Washington, D.C. August 1992, and at the Materials Research Society Meeting, Boston, November 1992. (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1275-1286 
    Details
    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 this work we report the effects of single stage zone drawing on the properties of NEW-TPI thermoplastic polyimide homopolymer, and its blends with Amoco's Xydar liquid crystalline polymer. Zone drawing was performed first on homopolymer NEW-TPI films to determine the effect of load weight, heater speed, and drawing temperature on the attainable draw ratio. Degree of crystallinity and chain orientation increase as the draw ratio increases for NEW-TPI. Blends of NEW-TPI/Xydar compositions 90/10 and 70/30 were studied next. In blends, the Xydar component is not molecularly dispersed, and is initially preferentially oriented along the machine direction during the film processing stage. Xydar acts as a nucleation site and lowers the temperature for crystallization of the NEW-TPI from the rubbery amorphous state. Zone drawing was performed either parallel or perpendicular to Xydar's initial preferred orientation direction. Blends with lower Xydar fraction could be zone-drawn to higher ratios. Zone drawing perpendicular to Xydar's initial orientation direction also resulted in increased draw ratio. Dynamic mechanical properties of the zone drawn materials were studied. In homopolymer NEW-TPI, dynamic modulus increased by a factor of two to 4.0 GPa in zone drawn films, largely as a result of the formation of oriented crystallites. In the blends, the modulus parallel to Xydar's initial orientation direction was greater than that in the transverse direction. Depending upon composition and test direction, zone drawing increased the dynamic moduli of the blends from 1.5 up to 2.7 times, in the temperature range from 150°C to 300°C.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341608
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    Processing/morphology correlations in poly(benzoate-co-naphthoate) liquid crystalline polymers (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1327-1335 
    Details
    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 molecular orientation and disclination defects in injection molded bulk samples of liquid crystal polymers have been revealed by transmission electron microscopy (TEM). Using a recently optimized lamellar decoration and etch technique for use with poly(benzoate-co-naphthoate), we have studied in detail the skin-core morphology produced by realistic injection molding processing. In the skin, the director is observed to be highly aligned along the flow direction, and the defect density is very low (10 cm-2). In the core, however, the defect density is six orders of magnitude greater, and the director lies predominantly in the plane defined by the flow and neutral directions. The flow during processing is turbulent, giving rise to distinct morphological features and disclination clusters. When the material is filled at 20% volume fraction with long glass fibers, the molecular and filler orientations are nearly parallel. Dimensional precision also correlates with the morphology and improves with increasing core fraction.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341705
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    Effect of grafting degree and side PEO chain length on the ionic conductivities of NBR-g-PEO based polymer electrolytes (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1305-1313 
    Details
    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: Comb-shaped graft polymers were synthesized and complexed with a LiCF3SO3 salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid 7Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341702
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  • 77
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    Thermal and mechanical properties of injection molded liquid crystalline polymer/amorphous polymer blends (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1336-1345 
    Details
    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 samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower-bound behavior that could be predicted by the one-adjustable-parameter equations of Halpin-Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self-reinforcement. APEC/LCP exhibited self-reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self-reinforcement was caused by the presence of an oriented LCP phase, confirmed by X-ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760341706
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    Solution structure of a core peptide derived from scyllatoxin (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 205-215 
    Details
    ISSN: 0887-3585
    Keywords: peptide folding ; disulfide framework ; insect toxins ; NMR ; distance geometry ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An analysis of the sequences of scyllatoxin and charybdotoxin suggested that it would be possible to design a core peptide sequence which would still fold to give the β-hairpin and helix seen in the toxins, but which would eliminate one disulfide and connecting residues. The core sequence was modeled, then synthesized and purified. The cysteines oxidize in air to give the same disulfide pairings as seen in the parent toxins as the major product. The three-dimensional structure of the core sequence peptide, termed Max, was determined using proton NMR spectroscopy and found to be identical in secondary structure to the toxins. However differences were found in the relative orientation of the β-hairpin and helix. The use of this structural motif, found in many insect toxins, as a disulfide framework for exploring sequence/structure/activity relationships is discussed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340180302
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  • 79
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    Thermodynamics of ubiquitin unfolding (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 246-253 
    Details
    ISSN: 0887-3585
    Keywords: microcalorimetry ; heat capacity ; enthalpy ; hydrogen bonding ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The energetics of ubiquitin unfolding have been studied using differential scanning microcalorimetry. For the first time it has been shown directly that the enthalpy of protein unfolding is a nonlinear function of temperature. Thermodynamic parameters of ubiquitin unfolding were correlated with the structure of the protein. The enthalpy of hydrogen bonding in ubiquitin was calculated and compared to that obtained for other proteins. It appears that the energy of hydrogen bonding correlates with the average length of the hydrogen bond in a given protein structure. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340180305
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  • 80
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    Hydrogen bond strength and β-sheet propensities: The role of a side chain blocking effect (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 262-266 
    Details
    ISSN: 0887-3585
    Keywords: protein structure prediction ; protein stability ; hydrogen bond ; β-sheet ; amino acid propensity ; steric effect ; hydrogen exchange ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Amino acid side chains can enhance peptide group hydrogen bond strength in protein structures by obstructing the competing hydrogen bond to solvent in the unfolded state. Available data indicate that the steric blocking effect contributes an average of 0.5 kJ per residue to protein hydrogen bond strength and accounts for the intrinsic α-sheet propensities of the amino acids. In available data for helical models, the contribution to α-helix propensities is obscured especially by large context-dependent effects. These issues are all related by a common side chain-dependent steric clash which disfavors peptide to water H-bond formation, peptide to catalyst complexation in hydrogen exchange reactions (Bai et al., Proteins 17:75-86, 1993), and peptide to peptide H-bonding in the helical main chain conformation (Creamer and Rose, Proc. Natl. Acad. Sci. U.S.A. 89:5937-5941, 1992) but not in α-strands. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340180307
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  • 81
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    A method for α-helical integral membrane protein fold prediction (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 281-294 
    Details
    ISSN: 0887-3585
    Keywords: membrane ; protein ; structure ; prediction ; G-protein coupled receptor ; rhodopsin ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Integral membrane proteins (of the α-helical class) are of central importance in a wide variety of vital cellular functions. Despite considerable effort on methods to predict the location of the helices, little attention has been directed toward developing an automatic method to pack the helices together. In principle, the prediction of membrane proteins should be easier than the prediction of globular proteins: there is only one type of secondary structure and all helices pack with a common alignment across the membrane. This allows all possible structures to be represented on a simple lattice and exhaustively enumerated. Prediction success lies not in generating many possible folds but in recognizing which corresponds to the native. Our evaluation of each fold is based on how well the exposed surface predicted from a multiple sequence alignment fits its allocated position. Just as exposure to solvent in globular proteins can be predicted from sequence variation, so exposure to lipid can be recognized by variable-hydrophobic (variphobic) positions. Application to both bacteriorhodopsin and the eukaryotic rhodopsin/opsin families revealed that the angular size of the lipid-exposed faces must be predicted accurately to allow selection of the correct fold. With the inherent uncertainties in helix prediction and parameter choice, this accuracy could not be guaranteed but the correct fold was typically found in the top six candidates. Our method provides the first completely automatic method that can proceed from a scan of the protein sequence databanks to a predicted three-dimensional structure with no intervention required from the investigator. Within the limited domain of the seven helix bundle proteins, a good chance can be given of selecting the correct structure. However, the limited number of sequences available with a corresponding known structure makes further characterization of the method difficult. © 1994 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340180309
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    Crystallization and preliminary crystallographic studies of the precursor and mature forms of a neutral lipase from the fungus Rhizopus delemar (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 301-306 
    Details
    ISSN: 0887-3585
    Keywords: triglyceride lipase ; proenzyme ; molecular replacement ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A neutral lipase from the filamentous fungus Rhizopus delemar has been crystallized in both its proenzyme and mature forms. Although the latter crystallizes readily and produces a variety of crystal forms, only one was found to be suitable for X-ray studies. It is monoclinic (C2, a = 92.8 Å, b = 128.9 Å, c = 78.3 Å, β = 135.8) with two molecules in the asymmetric unit related by a noncrystallographic diad. The prolipase crystals are orthorhombic (P212121, with a = 79.8 Å, b = 115.2 Å, c = 73.0 Å) and also contain a pair of molecules in the asymmetric unit. Initial results of molecular replacement calculations using the refined coordinates of the related lipase from Rhizomucor miehei identified the correct orientations and positions of the protein molecules in the unit cells of crystals of both proenzyme and the mature form. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340180311
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    Correlated mutations and residue contacts in proteins (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 309-317 
    Details
    ISSN: 0887-3585
    Keywords: protein structure prediction ; predicted contact maps ; correlated mutations ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The maintenance of protein function and structure constrains the evolution of amino acid sequences. This fact can be exploited to interpret correlated mutations observed in a sequence family as an indication of probable physical contact in three dimensions. Here we present a simple and general method to analyze correlations in mutational behavior between different positions in a multiple sequence alignment. We then use these correlations to predict contact maps for each of 11 protein families and compare the result with the contacts determined by crystallography. For the most strongly correlated residue pairs predicted to be in contact, the prediction accuracy ranges from 37 to 68% and the improvement ratio relative to a random prediction from 1.4 to 5.1. Predicted contact maps can be used as input for the calculation of protein tertiary structure, either from sequence information alone or in combination with experimental information. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340180402
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    Analysis of Cα geometry in protein structures (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 18 (1994), S. 324-337 
    Details
    ISSN: 0887-3585
    Keywords: protein structure ; secondary structure ; peptide geometry ; Ramachandran plot ; β-turns ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The polypeptide of a protein molecule can be considered as a chain of Cα atoms linked by pseudobonds between the Cα atoms of successive amino acid residues. This paper presents an analysis of the angle and dihedral angles made by these pseudobonds in protein structures determined at high resolution by X-ray crystallography. This analysis reveals a strong correlation between Cα geometry and the protein fold. The regular features of protein secondary structure such as α-helix and α-sheet are very clearly defined. In addition, it is possible to identify with some confidence the discrete populations of particular conformations of α-turn. Comparison with the traditional Ramachandran type of plot demonstrates that an analysis of protein structure on the basis of Cα geometry provides a richer description of protein conformation. In addition, the characteristics of this geometry could be a useful guide in model building of protein structure. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340180404
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    Crystallization of a fragment of human fibronectin: Introduction of methionine by site-directed mutagenesis to allow phasing via selenomethionine (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 48-54 
    Details
    ISSN: 0887-3585
    Keywords: X-ray crystallography ; extracellular matrix ; multiwavelength anomalous diffraction (MAD) ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Crystals of a fragment of human fibronectin encompassing the 7th through the RGD-containing 10th type III repeats (FN7-10) have been produced with protein expressed in E. coli. The crystals are monoclinic with one molecule in the asymmetric unit and diffract to beyond 2.0 Å Bragg spacings. A mutant FN7-10 was produced in which three methionines, in addition to the single native methionine already present, have been introduced by site-directed mutagenesis. Diffraction-quality crystals of this mutant protein have been grown in which methionine was replaced with selenomethionine. The introduction of methionine by site-directed mutagenesis to allow phasing from selenomethionyl-substituted crystals is shown to be feasible by this example and is proposed as a general approach to solving the crystallographic phase problem. Strategies for selecting propitious sites for methionine mutations are discussed. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340190107
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    Combining evolutionary information and neural networks to predict protein secondary structure (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 55-72 
    Details
    ISSN: 0887-3585
    Keywords: secondary structure prediction ; prediction of secondary structure class ; prediction of secondary structure content ; evolutionary information ; multiple alignment profiles ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Using evolutionary information contained in multiple sequence alignments as input to neural networks, secondary structure can be predicted at significantly increased accuracy. Here, we extend our previous three-level system of neural networks by using additional input information derived from multiple alignments. Using a position-specific conservation weight as part of the input increases performance. Using the number of insertions and deletions reduces the tendency for overprediction and increases overall accuracy. Addition of the global amino acid content yields a further improvement, mainly in predicting structural class. The final network system has a sustained overall accuracy of 71.6% in a multiple cross-validation test on 126 unique protein chains. A test on a new set of 124 recently solved protein structures that have no significant sequence similarity to the learning set confirms the high level of accuracy. The average cross-validated accuracy for all 250 sequence-unique chains is above 72%. Using various data sets, the method is compared to alternative prediction methods, some of which also use multiple alignments: the performance advantage of the network system is at least 6 percentage points in three-state accuracy. In addition, the network estimates secondary structure content from multiple sequence alignments about as well as circular dichroism spectroscopy on a single protein and classifies 75% of the 250 proteins correctly into one of four protein structural classes. Of particular practical importance is the definition of a position-specific reliability index. For 40% of all residues the method has a sustained three-state accuracy of 88%, as high as the overall average for homology modelling. A further strength of the method is greatly increased accuracy in predicting the placement of secondary structure segments. © 1994 Wiley-Liss, Inc.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340190108
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    Expression, purification, and crystallization of restriction endonuclease PvuII with DNA containing its recognition site (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 77-79 
    Details
    ISSN: 0887-3585
    Keywords: endonuclease overexpression ; crystallization ; X-ray diffraction ; protein-DNA complex ; Type II restriction enzyme ; vapor diffusion ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: We have overexpressed the type II restriction endonuclease PvuII (R.PvuII) in E. coli, prepared large amounts of the homogeneous enzyme, and crystallized it with an oligonucleotide carrying a PvuII recognition site. The cocrystals are orthorhombic space group P212121 with cell constants a = 95.8 Å, b = 86.3 Å, c = 48.5 Å, and diffract X-rays to at least 2.7 Å. There is a complex of two protein subunits and one oligonucleotide duplex in the asymmetric unit. © 1994 Wiley-Liss, Inc.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340190110
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    Masthead (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994) 
    Details
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340190201
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  • 89
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    Crystallization and preliminary X-ray crystallographic analysis of phospholipid transfer protein from maize seedlings (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 80-83 
    Details
    ISSN: 0887-3585
    Keywords: maize protein ; crystals ; X-ray diffraction ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Phospholipid transfer protein from maize seedlings has been crystallized using trisodium citrate as precipitant. The crystal belongs to the orthorhombic space group P212121 with unit cell dimensions of a = 24.46 Å, b = 49.97 Å, and c = 69.99 Å. The presence of one molecule in the asymmetric unit gives a crystal volume per protein mass (Vm) of 2.36 Å 3/Da and a solvent content of 48% by volume. The X-ray diffraction pattern extends at least to 1.6 Å Bragg spacing when exposed to both CuKα and synchrotron X-rays. A set of X-ray data to approximately 1.9 Å Bragg spacing has been collected from a native crystal. © 1994 Wiley-Liss, Inc.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340190111
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  • 90
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    α-Helix-forming propensities in peptides and proteins (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 85-97 
    Details
    ISSN: 0887-3585
    Keywords: protein conformation ; secondary structure ; protein folding ; helix stability ; helix formation ; conformational entropy ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Much effort has been invested in seeking to understand the thermodynamic basis of helix stability in both peptides and proteins. Recently, several groups have measured the helix-forming propensities of individual residues (Lyu, P. C., Liff, M. I., Marky, L. A., Kallenbach, N. R. Science 250:669-673, 1990; O'Neil, K. T., DeGrado, W. F. Science 250:646-651, 1990; Padmanabhan, S., Marqusee, S., Ridgeway, T., Laue, T. M., Baldwin, R. L. Nature (London) 344:268-270, 1990). Using Monte Carlo computer simulations, we tested the hypothesis that these differences in measured helix-forming propensity are due primarily to loss of side chain conformational entropy upon helix formation (Creamer, T. P., Rose, G. D. Proc. Natl. Acad. Sci. U.S.A. 89:5937-5941, 1992). Our previous study employed a rigid helix backbone, which is here generalized to a completely flexible helix model in order to ensure that earlier results were not a methodological artifact. Using this flexible model, side chain rotamer distributions and entropy losses are calculated and shown to agree with those obtained earlier. We note that the side chain conformational entropy calculated for Trp in our previous study was in error; a corrected value is presented. Extending earlier work, calculated entropy losses are found to correlate strongly with recent helix propensity scales derived from substitutions made within protein helices (Horovitz, A., Matthews, J. M., Fersht, A. R. J. Mol. Biol. 227:560-568, 1992; Blaber, M., Zhang, X.-J., Matthews, B. M. Science 260:1637-1640, 1993). In contrast, little correlation is found between these helix propensity scales and the accessible surface area buried upon formation of a model polyalanyl α-helix. Taken in sum, our results indicate that loss of side chain entropy is a major determinant of the helix-forming tendency of residues in both peptide and protein helices. © 1994 Wiley-Liss, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340190202
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    1.56 Å structure of mature truncated human fibroblast collagenase (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 98-109 
    Details
    ISSN: 0887-3585
    Keywords: crystallography ; hydroxamate ; high resolution ; metalloproteinase ; zinc ; X-ray ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The X-ray crystal structure of a 19 kDa active fragment of human fibroblast collagenase has been determined by the multiple isomorphous replacement method and refined at 1.56 Å resolution to an R-factor of 17.4%. The current structure includes a bound hydroxamate inhibitor, 88 waters and three metal atoms (two zincs and a calcium). The overall topology of the enzyme, comprised of a five stranded β-sheet and three α-helices, is similar to the thermolysin-like metalloproteinases. There are some important differences between the collagenase and thermolysin families of enzymes. The active site zinc ligands are all histidines (His-218, His-222, and His-228). The presence of a second zinc ion in a structural role is a unique feature of the matrix metalloproteinases. The binding properties of the active site cleft are more dependent on the main chain conformation of the enzyme (and substrate) compared with thermolysin. A mechanism of action for peptide cleavage similar to that of thermolysin is proposed for fibroblast collagenase. © 1994 Wiley-Liss, Inc.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340190203
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  • 92
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    Kinetic study on myoglobin refolding monitored by five optical probe stopped-flow methods (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 110-119 
    Details
    ISSN: 0887-3585
    Keywords: folding intermediate ; urea denaturation ; stopped-flow circular dichroism ; molten globule ; hemindicyanide ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The refolding kinetics of horse cyanometmyoglobin induced by concentration jump of urea was investigated by five optical probe stopped-flow methods: absorption at 422 nm, tryptophyl fluorescence at around 340 nm, circular dichroism (CD) at 222 nm, CD at 260 nm, and CD at 422 nm. In the refolding process, we detected three phases with rate constants of 〉 1 × 102 s-1, (4.5-9.3) S-1, and (2-5) × 10-3 s-1. In the fastest phase, a substantial amount of secondary structure (40%) is formed within the dead time of the CD stopped-flow apparatus (10.7 ms). The kinetic intermediate populated in the fastest phase is shown to capture a hemindicyanide, suggesting that a “heme pocket precursor” recognized by hemindicyanide must be constructed within the dead time. In the middle phase, most of secondary and tertiary structures, especially around the captured hemindicyanide, have been constructed. In the slowest phase, we detected a minor structural rearrangement accompanying the ligand-exchange reaction in the fifth coordination of ferric iron. We present a possible model for the refolding process of myoglobin in the presence of the heme group. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340190204
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    Decoupling of melting domains in immobilized ribonuclease A (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 120-131 
    Details
    ISSN: 0887-3585
    Keywords: enzymes ; protein immobilization ; microcalorimetry ; protein melting domains ; protein DSC ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Ribonuclease A has been immobilized on silica beads through glutaraldeyde-mediated chemical coupling in order to improve the stability of the protein against thermal denaturation. The thermodynamic and binding properties of the immobilized enzyme have been studied and compared with those of the free enzyme. The parameters describing the binding of the inhibitor 3′ -CMP (Ka and ΔH) as monitored by spectrophotometry and calorimetry were not significantly affected after immobilization. Conversely both the stability and unfolding mechanism drastically changed. Thermodynamic analysis of the DSC data suggests that uncoupling of protein domains has occurred as a consequence of the immobilization. The two state approximation of the protein unfolding process is not longer valid for the immobilized RNase. Protein stability strongly depends on the hydrophobicity properties of the support surface as well as on the presence of the inhibitor and pH. For example, after immobilization on a highly hydrophobic surface, the enzyme is partially in the unfolded state. The binding of a ligand is able to reorganize the protein structure into a native-like conformation. The refolding rates are different for the two protein domains and vary as a function of pH and presence of the inhibitor 3′-CMP. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340190205
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  • 94
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    Temperature-induced complementarity as a mechanism for biomolecular assembly (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 19 (1994), S. 73-76 
    Details
    ISSN: 0887-3585
    Keywords: molecular recognition ; protein assembly ; protein folding ; protein interactions ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Recent advances in the measurement and theory of “hydration” interactions between biomolecules provide a basis on which to formulate mechanisms of biomolecular recognition. In this paper we have developed a mathematical formalism for analyzing specificity encoded in dynamic distributions of surface polar groups, a formalism that incorporates newly recognized properties of directly measured “hydration” forces. As expected, attraction between surfaces requires complementary patterns of surface polar groups. In contrast to usual expectations, thermal motion can create these complementary surface configurations. We have demonstrated that assembly can occur with an increase in conformational entropy of polar residues. Elevated temperature then facilitates recognition rather than hinders it. This mechanism might underlie some temperature-favored assembly reactions common in biological systems that are usually associated with the “hydrophobic effect” only. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340190109
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    Coiled-coil stutter and link segments in keratin and other intermediate filament molecules: A computer modeling study (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994), S. 174-184 
    Details
    ISSN: 0887-3585
    Keywords: coiled-coils ; keratin ; intermediate filament proteins ; link segments ; heptad phasing ; computer modeling ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Structural discontinuities have previously been identified in four regions of the coiled-coil rod domain structure present in intermediate filament (IF) protein molecules. These include a point at which a phase shift occurs in the heptad periodicity characteristic of the sequence of polar and apolar residues in α-helical coiled-coils, and three links that lack a heptad substructure. We have studied these regions by computer-based molecular modeling and comparative sequence analysis and conclude that the phasing discontinuity can be accommodated without significant distortion of the overall double-helical chain conformation; the L2 link has a similar conformation in all different types of IF molecules, a favorable conformation being one in which the two strands wrap tightly around each other; the L12 links vary in length between different IF types but contain important sequence similarities suggestive of a partial β structure; the L1 links show larger variations in length, a lower degree of similarity, and probably diverse structures. Variations in the overall charges of the different links suggest that ionic interactions may playa significant role in filament assembly. The results also have general significance for other α-fibrous proteins in which either the characteristic heptad phasing undergoes a discontinuity or where a short non-coiled-coil sequence occurs within a coiled-coil rod domain structure. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340200207
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    Crystallization and characterization of the recombinant human Clara cell 10-kDa protein (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994), S. 191-196 
    Details
    ISSN: 0887-3585
    Keywords: human Clara cell 10-kDa protein ; X-ray diffraction ; phospholipase A2 inhibitor ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Crystals of recombinant human Clara cell 10-kDa protein were grown both from ammonium sulfate and polyethylene glycol (PEG) solutions. Crystals grown from ammonium sulfate solution have been characterized by X-ray diffraction studies as monoclinic with the space group C2 and lattice constants a = 69.2 Å, b = 83.0 Å, c = 58.3 Å, and β = 99.7°. The monoclinic crystals diffract to beyond 2.5 Å. Some of the crystals grown from PEG were of a similar habit to those grown from ammonium sulfate, but others were triclinic with the space group P1 and cell constants a = 40.3 Å, b = 46.3 Å, c = 51.3 Å, α = 117.7°, β = 102.3°, and γ = 71.4°. These crystals diffract to beyond 3.2 Å. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340200209
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    Conformational analysis of hemopexin by fourier-transform infrared and circular dichroism spectroscopy (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994), S. 185-190 
    Details
    ISSN: 0887-3585
    Keywords: heme ; secondary structure ; conformation ; hemopexin ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Hemopexin is a serum glyco-protein that binds heme with the highest known affinity of any characterized heme-binding protein and plays an important role in receptormediated cellular heme uptake. Complete understanding of the function of hemopexin will require the elucidation of its molecular structure. Previous analysis of the secondary structure of hemopexin by far-UV circular dichroism (CD) failed due to the unusual positive ellipticity of this protein at 233 nm. In this paper, we present an examination of the structure of hemopexin by both Fourier-transform infrared (FTIR) and circular dichroism spectroscopy. Our studies show that hemopexin contains about 55% β-structure, 15% α-helix, and 20% turns. The two isolated structural domains of hemopexin each have secondary structures similar to hemopexin. Although there are significant tertiary conformational changes indicated by the CD spectra, the overall secondary structure of hemopexin is not affected by binding heme. However, moderate changes in secondary structure do occur when the heme-binding domain of hemopexin associates with heme. In spite of the exceptionally tight binding at neutral pH, heme is released from the bis-histidyl heme-hemopexin complex at pH 5.0. Under this acidic condition, hemopexin maintains the same overall secondary structure as the native protein and is able to resume the heme-binding function and the native structure of the hemeprotein (as indicated by the CD spectra) when returned to neutral pH. We propose that the state of hemopexin identified in vitro at pH 5.0 resembles that of this protein in the acidic environment of the endosomes in vivo when hemopexin releases heme during receptor-mediated endocytosis. © 1994 Wiley-Liss, Inc.
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    URL: http://dx.doi.org/10.1002/prot.340200208
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    Masthead (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994) 
    Details
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340200301
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    Preliminary crystallographic analysis of an enzyme involved in erythromycin biosynthesis: Cytochrome P450eryF (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994), S. 197-201 
    Details
    ISSN: 0887-3585
    Keywords: cytochrome P450 ; erythromycin ; P450eryF ; crystallization ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Cytochrome P450eryF was overexpressed in Escherichia coli and purified in high yield. Crystals of the protein in the presence of the substrate, 6-deoxyerythronolide B, have been obtained by the hanging drop vapor diffusion method, using polyethylene glycol 4000 as a precipitant. The crystals belong to the orthorhombic space group P212121 with unit cell dimensions of a = 54.16 Å, b = 79.67 Å, and c = 99.48 Å and one molecule per asymmetric unit. A complete native data set has been collected to a resolution of 2.1 Å, and anomalous dispersion difference Patterson maps have revealed the location of the single heme iron atom. © 1994 Wiley-Liss, Inc.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/prot.340200210
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    Electronic Resource
    Electronic Resource
    Homology modeling of the Abl-SH3 domain (1994)
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 20 (1994), S. 203-215 
    Details
    ISSN: 0887-3585
    Keywords: SH3 ; Abl ; molecular modeling ; homology modeling ; molecular dynamics ; protein structure prediction ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A tertiary structure model of the Abl-SH3 domain is predicted by using homology modeling techniques coupled to molecular dynamics simulations. Two template proteins were used, Fyn-SH3 and Spc-SH3. The refined model was extensively checked for errors using criteria based on stereochemistry, packing, solvation free-energy, accessible surface areas, and contact analyses. The different checking methods do not totally agree, as each one evaluates a different characteristic of protein structures. Several zones of the protein are more susceptible to incorporating errors. These include residues 13, 15, 35, 39, 45, 46, 50, and 60. An interesting finding is that the measurement of the Cα chirality correlated well with the rest of the criteria, suggesting that this parameter might be a good indicator of correct local conformation. Deviations of more than 4 degrees may be indicative of poor local structure. © 1994 Wiley-Liss, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prot.340200302
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