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  • 2015-2019
  • 1990-1994  (24,488)
  • 1920-1924
  • Polymer and Materials Science  (21,194)
  • Chemical Engineering  (3,294)
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  • 101
    Electronic Resource
    Electronic Resource
    The biodegradation of polymers: Recent resultsPaper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 21-35 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general introduction including definition of biodegradability, the recent literature is briefly summarized. The results obtained in our laboratory for various polymers in three different composting units are then presented. They demonstrate that there is an urgent need for a quantitative method to characterize polymer biodegradation. For that purpose, a manometric method which allows the measurement of the oxygen consumed by the growing microorganisms has been developed. It has been tested with various inocula of increasing complexity: one Streptomyces sp., a mixture of three Streptomyces (badius, setonii and viridosporus), a compost extract or sewer sludge, growing in the presence of low molecular weight molecules as sole carbon source. Its performances and limitations are discussed. It is then applied to various polymer systems: polyesters and their constituent units, autoxidized polyethylene (APE) and its model compounds, polyvinyl alcohol (PVAl), starch and cellulose. The biodegradability of these polymers is characterized and their potential use as biodegradable materials for packaging, sanitary and agricultural uses is discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160102
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  • 102
    Electronic Resource
    Electronic Resource
    Cetylpyridinium chloride-modified poly(ethyleneimine) for the removal and separation of inorganic ions in aqueous solution (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 175-188 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Entfernung und Trennung einer Reihe von Metallionen mit Hilfe des wasserläoslichen Cetylpyridiniumchlorid-modifizierten Poly(ethylenimin)s (PEI-CPC) wurden in Kombination mit der Membranfiltration untersucht. Die Liquid-Phase Polymer-Based Retention(LPR)-Methode wurde zur Abtrennung von niedermolekularen Spezies beiverschiedenen pH-Werten und bei mehreren Elementkonzentrationen herangezogen. Die Studie umfaßt wäassrige Läosungen der Anionen Chromat und Phosphat sowie der Kationen Cu(II), Zn(II), Co(II), Ni(II), Cr(III), Fe(III), Cd(II), Pb(II) und Sr(II). Die Ergebnisse zeigen, daß eine hohe Retention für beide Anionen und auch für die meisten untersuchten Metallionen erzielt wurde. PEI-CPC zeigte gute Abtrenneigenschaften für Chromat-und Phosphationen selbst bei relativ hohen Anionenkonzentrationen 85 bzw. 150 mg · L-1und ebenso fäu die meisten untersuchten Metallionen. Im Falle der Cu(II)-, Ni(II)-und Sr(II)-Lonen wurde eine selektive Interaktion beobachtet. Das Polymerreagenz und seine Interaktionsprodukte wurden durch IR- und UV/Vis-Spektrometrie sowie Viskosimetrie charakterisiert. Zusäatzlich wurde das Interaktionsverhalten durch die Retentionsfäahigkeit untersucht. Eine gute Korrelation wurde zwischen den Retentionsdaten und den IR-und UV/VIS-Spektren der Interaktionsprodukte des Polymerreagenzes mit den Metallionen gefunden.
    Notes: The removal and separation of a series of ions by the water-soluble cetylpyridinium chloride-modified poly(ethyleneimine) (PEI-CPC) in conjunction with membrane filtration were investigated. The Liquid-Phase Polymer-Based Retention (LPR) method was applied to study the removal of the low-molecular species at different pH values and at several element concentrations. The study comprises aqueous solutions of the anions chromate and phosphate, and of the cations Cu(II), Zn(II), Co(II), Ni(II), Cr(III), Fe(III), Cd(II), Pb(II) and Sr(II). The results show that a high retention was attained in neutral solutions for both anions and also for most metal ions investigated. PEI-CPC exhibited good removing abilities for chromate and phosphate ions even at relatively high concentrations of anions (85 and 150 mg · L -1, respectively) and also for most of the metal ions studied. In the case of Cu(II), Ni(II), Cd(II), and Sr(II) ions, selective interactions were observed. The polymer reagent and its interaction products were characterized by IR, UV/VIS spectrometry, and viscometry. In addition, the interaction behaviour was investigated by the retention ability. A good correlation was found between the retention data and the IR and UV/VIS spectra of the interaction products of the polymer reagent with the metal ions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052150115
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  • 103
    Electronic Resource
    Electronic Resource
    Reaction of hals in polypropylene during light exposure: Part 1-iso-octane as reaction model compound -Paper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 101-112 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photo and thermal reactivity of nitroxyl radicals derived from di-, (oligo)meric hindered amine light stabilizers (HALS) on iso-octane, a model compound for polyprophylene, was studied and compared to that of monomeric 2,2,6,6-tetramethyl- piperi-dine-N-oxyl (TEMPO).The exchange-interaction among 〉N—O. groups seems to affect only the thermal process.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160107
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  • 104
    Electronic Resource
    Electronic Resource
    Application of chemiluminescence to polymer degradation studies. Thermal oxidation of polyamide 6.Paper presented at the “15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 2-4, 1993. (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 216 (1994), S. 169-186 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chemiluminescence (CL) technique was used to study the thermal oxidation of polyamide 6 samples with different ratio of terminal basic and acid groups, which perform a distinct effect on kinetics of the isothermal CL - time runs at 120-140°C. The isothermal experiments are complemented by nonisothermal ramp experiments where the CL intensity is monitored against temperature at a programmed rate of temperature increase.The relation of parameters such as initial CL intensity, integrated value of CL intensity for both isothermal and nonisothermal experiments and rate constants corresponding to CL - time curves was discussed within the results of other oxidation stability tests as absroption of oxygen, thermogravimetry, etc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052160112
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  • 105
    Electronic Resource
    Electronic Resource
    Modified styrene-isoprene-styrene block copolymer membranes complexed with cobalt-containing schiff's bases for oxygen permeation (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 31-41 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die strahleninduzierte Pfropfpolymerisation von 4-Vinylpyridin (VP) und 1 -Vinylimidazol (VIm) auf ein Styrol-Isopren-StyroI-Blockcopolymeres (SIS) sowie die Gasdurchlässigkeit von daraus hergestellten Membranen wurde untersucht. Eine Komplexierung der modifizierten SIS-Copolymeren (SIS-g-VP bzw. SIS-g-VIm) mit Cobalt enthaltenden Schiffschen Basen (CoS) als fixierte Sauerstoffträger verbesserte deren Sauerstoffdurchlässigkeit. Der Mechanismus des Sauerstofftransports wird diskutiert.
    Notes: The grafting of 4-vinylpyridine (VP) and 1-vinylimidazole (VIm) onto styrene-isoprene-styrene (SIS) triblock copolymer by radiation-induced graft copolymerization was studied. The effect of grafting degree on gas permeability of membranes made of grafted copolymers was investigated. The complex formation of the modified SIS (SIS-g-VP or SIS-g-VIm) with cobalt-containing Schiff's bases (CoS) in chloroform solution was studied. Facilitated transport of molecular oxygen in modified SIS membranes containing CoS as fixed carrier of oxygen, and oxygen permeability in modified SIS membranes due to the oxygen binding ability to CoS was observed. Mechanism of oxygen transport across the SIS-g-VP-CoS and SIS-g-VIm-CoS membrane is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052170104
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  • 106
    Electronic Resource
    Electronic Resource
    Electron beam initiated grafting of methyl methacrylate onto polyethylene: Structure and properties (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 61-69 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyethylen (PE, 100 Gew.-Teile) wurde mit Methylmethacrylat (MMA, bis zu 5 Gew.-Teilen) gemischt und anschließend mit Elektronen (bis zu 20 Mrad) bestrahlt, um PE/MMA-Pfropfcopolymere herzustellen, deren Bildung mittels IR-Spektroskopie nachgewiesen wurde. Gelbildung wies auf eine Vernetzung während der Bestrahlung hin. Zunehmende MMA-Konzentration und höhere Bestrahlungsdosen verringerten die Kristallit-Schmelztemperatur und den Kristallisationsgrad des PE. Zugfestigkeit, Bruchdehnung und Dielektrizitätskonstante wurden gemessen und diskutiert.
    Notes: Polyethylene (PE, 100 parts by weight) was mixed with methyl methacrylate (MMA, up to 5 parts by weight) at 120°C and subsequently exposed to electron radiation of different doses (up to 20 Mrad) to prepare PE/MMA graft copolymers. Successful grafting was verified by IR spectroscopy. Gel formation indicated crosslinking. Grafting increased with increasing MMA concentration and increasing irradiation dose. Crystalline melting temperature and percent crystallinity were lower than those of untreated PE. Tensile strength, elongation at break and dielectric constant of grafted samples were measured and discussed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052170107
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  • 107
    Electronic Resource
    Electronic Resource
    Reactive blending of thermosets: Molecular, morphological and mechanical analysis (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 159-190 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mit einer Reihe unterschiedlicher Methoden wurde versucht, die Zähigkeit tri- und tetrafunktioneller Epoxid- sowie ungesättigter Polyesterharze zu erhöhen. Die Epoxidharze wurden durch harte, thermisch stabile Konstruktionskunststoffe, ein Bisphenol-A Polycarbonat bzw. ein thermoplastisches Polyetherimid (Ultem 1000), modifiziert. Bei den ungesättigten Polyesterharzen wurde ein anderes Verfahren angewendet: Zwei handelsübliche flüssige Kautschuke wurden chemisch modifiziert, um ihre Reaktivität gegenüber den funktionellen Gruppen der Matrix zu steigern: Ein hydroxyterminiertes Polybutadien und ein aminoterminiertes Butadien-Acrylnitril-Copolymeres wurden zu Polymeren mit Isocyanat- bzw. Maleimidendgruppen umgesetzt. Ein weiteres hier beschriebenes System zielt darauf ab, die rasch abnehmende Steifheit der Polyestermatrix bei Temperaturen oberhalb Raumtemperatur zu verringern. Dazu wurde ein hitzehärtbares Bismaleimidharz als zweite co-reaktive Komponente in den Polyester eingebracht.
    Notes: A number of different approaches were used to enhance the toughness of tri- and tetrafunctional epoxies and of unsaturated polyester resins. In the case of epoxies, tough, thermally stable, engineering thermoplastics, namely a bisphenol-A polycarbonate and a thermoplastic poly(ether imide) (Ultem 1000) were employed as modifiers. For unsaturated polyesters a different approach was adopted: two commercial liquid rubbers were chemically modified to enhance their reactivity towards the matrix functionalities. In particular, a hydroxy-terminated polybutadiene and an aminoterminated butadiene-acrylonitrile copolymer were transformed into isocyanate-terminated and maleimide-terminated rubbers, respectively. A further system which is described in the present contribution is aimed at mitigating another deficiency of the polyester matrix, namely its rapidly decreasing rigidity at temperatures above room temperature. In this case, a thermosetting bismaleimide was incorporated into the resin as a co-reactive second component.
    Additional Material: 28 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052170115
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  • 108
    Electronic Resource
    Electronic Resource
    Recycling of egyptian bagasse pith wastes in the synthesis of cationic resins (1994)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 1-10 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe sulfonierter kationischer m-Kresol-Paraformaldehyd-Harze wurden aus dem Mark ägyptischer Bagasse hergestellt. Reaktionsbedingungen werden angegeben, und die Eigenschaften der hergestellten Bagassemark/m-Kresol/Formaldehyd-Harze werden mit denen von Harzen ohne Bagassemark verglichen. Die synthetisierten Polymere sind stabil in Wasser, verdünnten Mineralsäuren (1 M) und organischen Lösungsmitteln sowie gegenüber thermischer Behandlung. Die Harze besitzen Kationenaustauscherkapazitäten von bis zu 2,91 meq/g (bezogen auf trockenes Harz) und werden als Austauschermaterialien für eine mögliche Trennung zweiwertiger Kationen getestet.
    Notes: A series of sulfonated cationic resins have been prepared and characterized from Egyptian bagasse pith wastes (as a source of cheaper and renewable material) with m-cresol and paraformaldehyde as a crosslinking agent. Reaction conditions for the preparation are presented and properties of the synthesized sulfonated bagasse pith-m-cresol-formaldehyde resins are described and compared with resin not containing bagasse pith. The synthesized resins are stable in water, dilute mineral acids (1 M), organic solvents, and to thermal treatment. The resins having a cation exchange capacity up to 2.91 meq g-1 of dry resin, are being introduced as new exchangers. The synthesized resins are used in the study of the possible separation of some bivalent cations.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1994.052180101
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  • 109
    Electronic Resource
    Electronic Resource
    Condensation of DNA by basic protiens does not depend on protien composition (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 285-292 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied by electron microscopy the size and morphology of the complexes obtained with different DNAs (between 500 and 5243 base pairs long) and four different proteins: sea urchin histone H1; sea cucumber histone φ0, chicken erythrocyte histone H5, and clupeine. Surprisingly, the type of protein used has only a marginal influence on the complexes formed. The molecular weight and topology of DNA do not show any influence. The size of the complexes depends strongly on the ratio of positive to negative charges and also on the ionic conditions. Our studies have been mainly carried out at a ratio of 0.4. Under these conditions the average thickness of rods and toroids observed varies between 165 Å at 1.5 mM salt to 290 Å at 100 mM salt, with minor variations around these values depending on the type of DNA and protein used. We conclude that the formation of DNA condensates is mainly determined by a balance of electrostatic and intermolecular forces, the influence of specific interactions is only marginal. This conclusion seems to apply not only to the complexes described here, but also to chromatin fibers and to DNA condensed by low molecular weight counterions and other compounds (polyamines, inorganic ions, ethanol, etc.). © 1994 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340214
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  • 110
    Electronic Resource
    Electronic Resource
    Vacuum-UV CD spectrum of the X-form of double-stranded poly(dA-dT) (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 299-301 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340216
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  • 111
    Electronic Resource
    Electronic Resource
    Thermodynamics of cyclophilin catalyzed peptidyl-prolyl isomerization by nmr spectroscopy (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 171-175 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One-dimensional nmr exchange spectroscopy was carried out to determine thermodynamic parameters of cyclophilin-induced cis-trans isomerization of succinyl-Ala-Phe-Pro-Phe-p-nitroanilide. Rate measurements were possible at physiological temperatures. The kc/Km of rat cyclophilin was found to he 12.8 (±0.5) s-1 μM-1 at 37°C, intermediate to previously reported values that used a coupled enzyme assay extrapolated to this temperature. Activation energies (ΔG≠) for the uncatalyzed and catalyzed reaction at 37°C were found to be 19.7 and 17.1 kcal/mol, respectively, and were primarily due to an enthalpic barrier. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340203
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  • 112
    Electronic Resource
    Electronic Resource
    Discontinuous volume transitions induced by calcium-sodium ion exchange in anionic gels and their neurobiological implications (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 209-215 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Discontinuous volume transitions in poly(acrylic acid) gels were studied by determining equilibrium swelling curves of small gel beads immersed in salt solutions containing varying concentrations of Ca2+ and Na+. Reversible contractions of gel membranes associated with Ca2+-Na+ exchange were examined using both isometric and isotonic recording devices. A discontinuous change in electric conductance was demonstrated in association with Ca2+-Na+ exchange in gel membranes. These experimental findings provide a sound physicochemical basis for elucidating the mechanism of nerve excitation. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340207
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  • 113
    Electronic Resource
    Electronic Resource
    Specificity of trypsin digestion and conformational flexibility at different sites of unfolded lysozyme (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 217-226 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourteen tryptic peptides and nine intermediates were identified as products of trypsin digestion of reduced and S-3-(trimethylated amino) propylated lysozyme. Kinetics of the appearance and disappearance of these products were observed by monitoring the peak areas on the chromatogram. In spite of the complicated reaction pathways, kinetics of the digestion of proteins and several intermediate products show simple decay curves with a single rate constant. In this paper, the trypsin susceptibility of the individual cleavage site is defined as a hydrolytic rate constant of the susceptible peptide bond in the presence of 10 nM trypsin. The cleavage sites of unfolded lysozyme are classified into two groups in terms of the trypsin susceptibility: one has a high susceptibility (10-20 h-1) and the other a low susceptibility (1.0-2.0 h-1). In the unfolded state of lysozyme, in conclusion, the region from residues 15 to 61 has a strong resistance to trypsin digestion; on the other hand, the C-terminal half of the polypeptide chain is flexible enough to fit into the active site of trypsin.In addition, six kinds of pentapeptides were synthesized as analogues of lysozyme fragments including Arg 14, Arg 21, Lys 33, Arg 45, Arg 61, and Arg 73. Kinetics of typtic digestion of them were observed. Both kcat and KM were determined for these synthetic pentapeptides. The susceptibility of each cleavage site in pentapeptides is determined and compared with that corresponding in proteins. The susceptibility is usually higher when the susceptible peptide chain is flexible. However, susceptibilities of a few sites in proteins are lower than those in pentapeptides. This means that the peptapeptides, this means that the peptide chains tend to fold locally to prevent trypsin from binding to the sites. It was found that the sites of Arg 21 and Arg 45 are indeed resistant to trypsin, but the site of Lys 33 is not so much, although the hydrolytic rate at Lys 33 itself is extremely slow. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360340208
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  • 114
    Electronic Resource
    Electronic Resource
    Electrophoretic mobility of DNA in gels. I. New biased reptation theory including fluctuations (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 239-247 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In weak electric fields, the motion of DNA molecules undergoing gel electrophoresis may be described by biased reptation. We argue that the degree of molecular orientation induced by the field is determined by a competition between longitudinal fluctuations and drift of the molecule along the tube. A self-consistent calculation shows that the end-to-end vector of long molecules varies with the square root of the field strength, and not linearly as previously supposed. This leads to a number of new predictions about the field dependence of the molecular mobility and the size limit of resolution. We present the results of computer simulations that support the predictions of the theory of biased reptation including fluctuations. Finally, we discuss the correspondence with experimental data and the implications of our findings for the optimization of DNA electrophoresis. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340210
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  • 115
    Electronic Resource
    Electronic Resource
    Electrophoretic mobility of DNA in gels. II. Systematic experimental study in agarose gels (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 249-259 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic study has been undertaken to prove or disprove the predictions of a revised reptation model, biased reptation with fluctuations (BRF). Our data, which scan about two orders of magnitude of DNA sizes and of electric fields, and a fourfold range of gel concentrations, are in qualitative and quantitative agreement with the model and support the applicability of this theory to DNA gel electrophoresis. In particular, we show that the mobility in the compression zone scales as the first power of the electric field, and that the limit of separation scales as the inverse first power of the electric field, for low enough fields. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340211
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  • 116
    Electronic Resource
    Electronic Resource
    Monte Carlo and Poisson-Boltzmann calculations of the fraction of counterions bound to DNA (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 227-237 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The counterion density and the condensation region around DNA have been examined as functions of both ion size and added-salt concentration using Metropolis Monte Carlo (MC) and Poisson-Boltzmann (PB) methods. Two different definitions of the “bound” and “free” components of the electrolyte ion atmosphere were used to compare these approaches. First, calculation of the ion density in different spatial regions around the polyelectrolyte molecule indicates, in agreement with previous work, that the PB equation does not predict an invariance of the surface concentration of counterions as electrolyte is added to the system. Further, the PB equation underestimates the counterion concentration at the DNA surface, compared to the MC results, the difference being greatest in the grooves, where ionic concentrations are highest. If counterions within a fixed radius of the helical axis are considered to be bound, then the fraction of polyelectrolyte charge neutralized by counterions would be predicted to increase as the bulk electrolyte concentration increases.A second categorization - one in which monovalent cations in regions where the average electrostatic potential is ledd than -kT are considered to be bound - provides an informative basis for comparison of MC and PB with each other and with counterion-condensation theory. By this criterion, PB calculations on the B from of DNA indicate that the amount of bound counterion charge per phosphate group is about .67 and is independent of salt concentration. A particularly provocative observatiob is that when this binding criterion is used, MC calculations quantitatively reproduce the bound fraction predicated by counterion-condensation theory for all-atom models of B-DNA and A-DNA as well as for charged cylindera of varying lineat charge densities. For example, for B-DNA and A-DNA, the fractions of phosphate groups neutralized by 2 Å hard sphere counterions are 0.768 and .817, respectively. For theoretical studies, the rediys enclosing the region in which the electrostatic potential is calculated studies, the radius enclosing the region in which the electrostatic potential is calculated to be less than -kT is advocated s a more suitable binding or condensation radius that enclosing the fraction of counterions given by (1 - ξ-1). A comparsion of radii calculated using both of these definitions is presented. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340209
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  • 117
    Electronic Resource
    Electronic Resource
    Change in mobility of side chains due to neutralization of charged poly(L-lysine) with dansyl group (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 101-108 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(L-lysine) having dansyl (5-dimethylamino-1-naphthalene-sulfonyl) groups to its side chains was prepared. The fluorescence spectra and fluorescence anisotropy ratios of the dansyl (DNS) group were measured in various conditions. In aqueous solution the increase in emission intensity was observed reflecting the alkali-induced coil-to-helix transition. In aqueous-methanolic solutions with methanol content above 60 wt %, the poly(L-lysine) with DNS group (DNS-PLL) was probed to show α-helical conformation from CD spectra. With addition of alkali, the increase in fluorescence intensity of α-helical DNS-PLL and the drastic change in fluorescence anisotropy ratio were observed. In this case the rotational mobility of DNS probe decreases, gives a minimum at a certain concentration of added alkali, and then increases again up to approximately the initial level. At the concentration where the rotational mobility gives the minimum, intensity of scattered light gives a maximum. This shows that suppression of the mobility of DNS side chains is caused by the intermolecular aggregation of α-helical DNS-PLL. This concentration of added alkali corresponds to the midpoint of neutralization to charged side chains of the DNS-PLL. The interaction that causes aggregate of α-helical DNS-PLL is suggested to be the intermolecular hydrogen bonding between neutralized and unneutralized side chains. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340111
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    Spatial translational motions of base pairs in DNA molecules: Application of the extended matrix generator method (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 121-142 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used the elementary generator matrices outlined in the preceding paper to examine the conformational plasticity of the nucleic acid double helix. Here we investigate kinked DNA structures made up of alternating B- and A-type helices and intrinsically curved duplexes perturbed by the intercalation of ligands. We model the B-to-A transition by the lateral translation of adjacent base pairs, and the intercalation of ligands by the vertical displacement of neighboring residues. We report a complete set of average configuration-dependent parameters, ranging from scalars (i.e., persistence lengths) to first- and second-order tensor parameters (i.e., average second moments of inertia), as well as approximations of the associated spatial distributions of the DNA and their angular correlations. The average structures of short chains (of lengths less than 100 base pairs) with local kinks or intrinsically curved sequences are essentially rigid rods. At the smallest chain lengths (10 base pairs), the kinked and curved chains exhibit similar average properties, although they are structurally perturbed compared to the standard B-DNA duplex. In contrast, at lengths of 200 base pairs, the curved and kinked chains are more compact on average and are located in a different space from the standard B- or A-DNA helix. While A-DNA is shorter and thicker than B-DNA in x-ray models, the long flexible A-DNA helix is thinner and more extended on average than its B-DNA counterpart because of more limited fluctuations in local structure. Curved polymers of 50 base pairs or longer also show significantly greater asymmetry than other DNAs (in terms of the distribution of base pairs with respect to the center of gravity of the chain). The intercalation of drugs in the curved DNA straightens and extends the smoothly deformed template. The dimensions of the average ellipsoidal boundaries defining the configurations of the intercalated polymers are roughly double those of the intrinsically curved chain. The altered proportions and orientations of these density functions reflect the changing shape and flexibility of the double helix. The calculations shed new light on the possible structural role of short A-DNA fragments in long B-type duplexes and also offer a model for understanding how GC-specific intercalative ligands can straighten naturally curved DNA. The mechanism is not immediately obvious from current models of DNA curvature, which attribute the bending of the chain to a perturbed structure in repeating tracts of A · T base pairs. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340113
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    Conformational analysis of chitobiose and chitosan (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 203-208 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relaxed potential energy surfaces of chitobiose were calculated based on the MM3-force field by optimizing dimer structures on a 10° grid spacing of the torsional angles about the glycosidic bonds (Φ,Ψ). The 36 conformations; the four combinations of the hydroxymethyl group orientations coupled with the nine of the secondary group ones -  were assumed for each Φ,Ψ conformation. The four conformations, each differing in the hydroxymethyl group orientations, were considered for the whole Φ,Ψ space, and all the 36 conformations, for the restricted space of low energy. While the resulting energy map and the structures of the energy minima were similar to those proposed for cellobiose in many respects, more restricted energy profile was suggested for the relaxed map of chitobiose where differences in the energy level between the global minimum and the local minima were within 5.4 kcal/mol, compared with the equivalent value of 3.6 kcal/mol for cellobiose. Further depression of the global minimum occurred when the acidic residue was used. The Monte Carlo samples of the chitosan chain were generated based on the relaxed map to predict the unperturbed coil dimension in solution. The chitosan chains showed Gaussian behavior at x = 500 (x, degree of polymerization) and gave the characteristic ratio Cx, of about 70, which was much larger than the experimental values observed for the chitosan and cellulosic chains. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340206
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    Three-dimensional Hartree-Fock crystal-orbital calculation on crystalline diprotonated deoxycytidine-5′-monophosphate monohydrate: Toward rationalizing nucleic acid semiconductivity (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 921-932 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A three-dimensional Hartree-Fock crystal-orbital calculation on the crystal of diprotonated deoxycytidine-5′-monophosphate monohydrate has been carried out using the CRYSTAL92 routine package. According to the calculation, this crystallohydrate can be considered a quasi one-dimensional hole semiconductor with the indirect fundamental gap of 1.66 eV and with a possibility for the uv-excited quasi one-dimensional electron photoconductivity. The physical source for such properties is the charge transfer from the phosphate to the water molecule and cytosine residue, favored by the strong electrostatic interaction between nucleotide zwitterions and by the formation of the infinite spirals of hydrogen-bonded zwitterions along one of the crystallographic axes. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340710
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    A CD study of the α-helix nucleation hypothesis (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 969-973 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One of the dilemmas in predicting the secondary structure of proteins from their amino acid propensity for a given conformation is the presence of all amino acids in all types of secondary structure, regardless of their propensity for that specific structure. One explanation is the nucleation hypothesis that only a few residues with a strong propensity for the secondary structure, such as the α-helix structure, initiates its formation and propagates the structure through indifferent sequences until strong breakers terminate the growth on both ends. Eight 15-mer peptides were studied to examine the α-helix nucleation hypothesis. The nucleation sequence of VAEAK, with high helix propensity, was mixed with an indifferent sequence of TSDSR in all possible permutations. From the percent α-helix structure derived from the CD at 222 nm, it appears that helicity does not propagate through the indifferent sequence. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340715
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    Thermodynamic basis of site-specific cooperativity (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1001-1005 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cooperative phenomena in biological macromolecules arise from the interaction of many distinct subsystems, such as structural domains or binding sites. Cooperative properties of the system as a whole, like protein folding or allosteric transitions, are subject to the restrictions imposed by thermodynamic stability. These restrictions, however, do not apply in the case of individual subsystems open to interactions with the rest of the macromolecule. The site-specific properties of such subsystems can be understood in general thermodynamic terms from those of a multicomponent system under particular conditions. The analogy provides a thermodynamic basis for site-specific Cooperativity. © 1994 John Wiley & Sons, Inc.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340803
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    Conformation and sweet tastes of L-aspartyl dipeptide methyl esters (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1037-1048 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to investigate the conformational preferences to elicit tastes, conformational free energy calculations using an empirical potential (ECEPP/2) and the hydration shell model were carried out on the L-aspartyl dipeptide methyl esters, L-+HAsp--L-Xaa-OMe, in the hydrated state, where Xaa includes sweet (Phe, Tyr, Met, and Gly), bitter (Ala, Trp, Val, Leu, and Ile), and tasteless (Ser, Thr, and Abu) residues. The refined preferred conformation of the Phe dipeptide (aspartame) with side chain χ21 conformation g- is g-Fg- in the hydrated state, which is consistent with the structure deduced from 1H-nmr experiments. Irrespective of the Xaa and taste, all the dipeptides have the same conformation for the Asp residue, which is attributable to the hydrogen bond between protonated amino hydrogen and carboxylate oxygen and the favored hydration of the carboxylate group. This implies that the L-aspartyl residue is a necessary factor for the dipeptides to be sweet not a sufficient factor. The computed conformational preferences for sweet, bitter, and tasteless dipeptides in the hydrated state indicate to us that the conformation about the N—Cα bond of the Xaa residue, i.e., the orientation of the hydrophobic moiety with respect to the AH/B functionalities in the aspartyl moiety, seems to be crucial to elicit the tastes. In addition, the hydrophobicity and the size of the Xaa residue are found to play a major role in determining the tastes. These well accord with the related works reported previously. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340807
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    Comparative interactions of magnesium and calcium counterions with polygalacturonic acid (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1059-1064 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The comparative interaction of Mg2+ and Ca2+ counterions on carboxyl groups of polygalacturonic acid is developed. Ultracentrifugation, conductimetry, potentiometry, and CD were used in this work. Evidence is provided for a simple electrostatic interaction of Mg2+ counterions; on the opposite side, cooperative interaction of Ca2+ counterions is again demonstrated, causing chain-chain association. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340809
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    The amplitude of local angular motion of purines in DNA in solution (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 463-480 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nuclear magnetic resonance and optical experiments are combined to determine the rms amplitude of local angular motion of purines in DNA in solution. A 12 base-pair duplex DNA with the sequence d (CGCGAATTCGCG)2 is deuterated at the H8 positions of adenine and guanine by exchange with solvent dklstwxzat 55°C. The deuterium nmr spectrum of this DNA is measured at 30 mg/mL at 30°C in an 11.76 Tesla magnet (76.75 MHz). The time-resolved fluorescence polarization anisotropies (FPA) of this same sample and also a greatly diluted sample (0.215 mg/mL) were measured after addition of ethidium. FPA measurements of the dilute sample yield the hydrodynamic radius, RH = 9.94 ± 0.2 Å, while those at the nmr concentration are employed to characterize the collective motions in terms of either an enhanced viscosity or dimer formation. The rms amplitude of local angular motion was determined by analyzing the 2H-nmr spectrum, in particular the line width, using recently developed theory for the transverse relaxation rate (R2Q) together with essential information about the collective motions from these and other optical studies. When the principal-axis frame of the electric field gradient tensor is assumed to undergo overdamped libration around each of its three body-fixed axes in an isotropic deflection potential, then the rms amplitude of local angular motion around any single axis is found to lie in the range 10°-11°, provided the high DNA concentration acts to enhance the viscosity, and is about 9°-11°, if it acts to produce end-to-end dimers. The proton nmr relaxation data of Eimer et al. are reanalyzed and shown to yield an rms amplitude of angular motion of the cytosme H5-H6 internuclear vector of 9°-10°, depending upon its orientation with respect to the helix axis. In all of these analyses, full account is taken of the collective twisting and bending deformations, which have a small but significant effect on the results. It is shown that the rms amplitudes of local angular motion do not depend strongly on the model (potential), provided that isotropic rotation around the same number of axes is allowed and that one compares rms angles of the same dimensionality. The rms amplitudes of local angular motion in solution are comparable to those observed for the same sequence at low levels of hydration in the solid state. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340404
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    Solution structure and dynamics of a glycoinositol phospholipid (GIPL-6) from Leishmania major (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1155-1163 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By use of a combination of 1H nuclear Overhauser effect measurements, restrained molecular dynamics simulations, and 13C spin-lattice relaxation time measurements, the solution behavior of the glycan moiety of a complex glycoinositol phospholipid termed G1PL-6, from the protozoan parasite Leishmania major has been determined. The glycan moiety of GIPL-6 has the following structure, which is characterized by the presence of an internal β-galactofuranose residue: The glycan does not adopt a single conformation in solution, due to significant torsional variations about the two phosphodiester linkages and certain glycosidic linking in the molecule. The present of the internal galactofuranose residue results in an average solution conformation of the oligosaccharide, which resembles a “hairpin,” with the galactofuranose residue at the apex. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340905
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    Theoretical conformational analysis of the opioid δ antagonist H-Tyr-Tic-Phe-OH and the μ agonist H-Tyr-D-Tic-Phe-NH2 (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1213-1219 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular mechanics study (grid search and energy minimization) of the highly δ receptor-selective δ opioid antagonist H-Tyr-Tic-Phe-OH (TIP; Tic: tetrahydroisoquinoline-3-car-boxylic acid) resulted in four low energy conformers with energies within 2 kcal/mol of that of the lowest energy structure. These four conformers contain trans peptide bonds only and represent compact structures showing various patterns of aromatic ring stacking. The centrally located Tic residue imposes several conformational constraints on the N-terminal dipeptide segment; however, the results of molecular dynamics simulations indicated that this tripeptide still shows some structural flexibility, particularly at the Phe3 residue. Analogous studies performed with the structurally related μ receptor-selective μ agonist H-Tyr-D-Tic-Phe-NH2 resulted in low energy structures that were also compact but showed patterns of ring stacking different from those obtained with TIP. Superim-position of low energy conformers of TIP and H-Tyr-D-Tic-Phe-NH2 revealed that the Phe3 residues of the L-Tic- and the D-Tic peptide were always located on opposite sides of the plane defined by the Tic residue, thus providing an explanation for the distinct activity profiles of the two compounds in structural terms. Attempts to demonstrate spatial overlap between the pharmacophoric moieties of low energy conformers of TIP and the nonpeptide δ antagonist naltrindole were made by superimposing either the Tyr1 and Tic2 aromatic rings and the N-terminal amino group or the Tyr1 and Phe3 aromatic rings and the N-terminal amino group of the peptide with the corresponding aromatic rings and nitrogen atom in the alkaloid structure. In each case a low energy structure of TIP was found that showed good spatial overlap of all three specified pharmacophoric groups. These two conformers may represent candidate structures for the δ receptor-bound conformation of TIP. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340909
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    Relaxed-residue conformational mapping of the three linkage bonds of isomaltose and gentiobiose with MM3(92) (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 625-638 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isoenergy surfaces were calculated for the α- and β-anomers of isomaltose and gentiobiose, based on 46,656 conformers for each disaccharide. Low-energy regions exist for each of the three staggered positions about the C-5′ — C-6′ bonds, and known crystal structures lie in two of these regions. As expected, the molecular partition function showed greater flexibility for these three-bond-linked disaccharides than for comparable two-bond-linked structures. A model miniature crystal of gentiobiose accounts for most of the remaining structural differences between the modeled isolated molecule and the crystal structure. Based on models of isolated molecules of isomaltose and gentiobiose, the predicted Boltzmann-weighted nmr coupling constants were satisfactory, as were predicted optical rotations for gentiobiose. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340505
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    On higher buckling transitions in supercoiled DNA (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 565-597 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A combination of detailed energy minimization and molecular dynamics studies of closed circular DNA offers here new information that may be relevant to the dynamics of short DNA chains and/or low superhelical densities. We find a complex dependence of supercoiled DNA energies and geometries on the linking number difference ΔLk as physiological superhelieal densities (|σ| ∼ 0.06) are approached. The energy minimization results confirm and extend predictions of classical elasticity theory for the equilibria of elastic rods. The molecular dynamics results suggest how these findings may affect the dynamics of super-coiled DNA.The minimization reveals sudden higher order configurational transitions in addition to the well-known catastrophic buckling from the circle to the figure-8. The competition among the bending, twisting, and self-contact forces leads to different families of supercoiled forms. Some of those families begin with configurations of near-zero twist. This offers the intriguing possibility that nicked DNA may relax to low-twist forms other than the circle, as generally assumed. Furthermore, for certain values of ΔLk, more than one interwound DNA minimum exists. The writhing number as a function of ΔLk is discontinuous in some ranges; it exhibits pronounced jumps as ΔLk is increased from zero, and it appears to level a characteristic slope only at higher values of ΔLk. These findings suggest that supercoiled DNA may undergo systematic rapid interconversions between different minima e both close in energy and geometry.Our molecular dynamics simulations reveal such transitional behavior. We observe the macroscopic bending and twisting fluctuations of interwound forms about the global helix axis as well as the end-over-end tumbling of the DNA as a rigid body. The overall mobility related to |σ| and to the bending, twisting, and van der Waals energy fluctuations. The general character of molecular motions is thus determined by the types of energy minima found at a given ΔLk. Different time scales may be attributed to each type of motion: The overall chain folding occurs on a time scale almost an order of magnitude faster than the end-over-end tumbling. The local bending and twisting of individual chain residues occur at an even faster rate, which in turn correspond to several cycles of local variations for each large-scale bending and straightening motion of the DNA. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360340502
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    Masthead (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360340601
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    Effects of DNA charge and length on the electrophoretic mobility of intercalated DNA (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1349-1358 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA molecules ranging in size from 1 to 630 kilobase pair and intercalated with either ethidium bromide (EtBr) or propidium iodide (PI) were electrophoresed in 1% agarose at four different electric field strengths. The extent of intercalation of EtBr under the conditions of our electrophoresis experiments was determined by a spectroscopic technique, whereas the extent of intercalation of PI was inferred from previous studies. The effects of the increase in DNA contour length and the concomitant decrease of linear charge density were separated based on our analysis of the mobility data. We conclude that the main factor responsible for the reduced electrophoretic mobility of intercalated DNA is the diminished linear charge density and not the increased contour length. © 1994 John Wiley & Sons, Inc.
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    The potential energy surface of methyl 3-O-(α-D-mannopyranosyl)-α-D-mannopyranoside in aqueous solution: Conclusions derived from optical rotation (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1395-1401 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical rotation of methyl 3-O -(α-D-mannopyranosyl)-α-D-mannopyranoside is calculated semiempirically as a function of the linkage dihedral angles φ (H1-C1-O1-C3′) and ψ (C1-O1-C3′-H3′). Comparison with the observed optical rotation in aqueous solution indicates the existence of at least two conformers in solution, which implies a degree of linkage flexibility. The result is in agreement with some, but not all, calculated potential energy surfaces, and with recently published nmr data. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360341010
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    Defect peptide chemistry: Perturbations in the structure of a homopentapeptide induced by a guest residue interrupting side-chain regularityDedicated to Prof. Murray Goodman on the occasion of his 65th birthday. (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1409-1418 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fully blocked pentapeptide Tfa-(Deg)2-L-Abu-(Deg)2-OtBu (Tfa:triflouroacetyl; Deg: Cα,α-diethylglycine; OtBu: tert-butoxy) adopts in the crystal state a regular, right-handed 310-helical structure stabilized by three N — H … O = C intramolecular 1 ← 4 (or C10) H bonds, as determined by an x-ray diffraction analysis. However, a Fourier transform ir absorption and 1H-nmr study strongly supports the view that in deuterochloroform solution the four Deg residues at both termini of the peptide main chain are involved in successive, fully extended C5 forms. A comparison with the stable, fully developed, multiple C5 conformation of Tfa-(Deg)5-OtBu indicates that incorporation of an Abu guest residue, interrupting the side-chain uniformity of the host (Deg)5 homopeptide, while altering only marginally the conformation in a solvent of low polarity, is responsible for a dramatic perturbation of the crystal-state structure. © 1994 John Wiley & Sons, Inc.
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    URL: http://dx.doi.org/10.1002/bip.360341012
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    A crystal structure with features of an antiparallel α-pleated sheet (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1463-1468 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A single-crystal x-ray diffraction analysis of Boc-L-Ala-D-aIle-L-Ile-OMe has been carried out. The analysis has shown (a) that the tripeptide molecules have in part an α-extended conformation, the torsion angles of the L-Ala and D-aIle residues being ϕ1 = -75.1° and ψ1 = -25.8° and ϕ2 = 67.3° and ψ2 = 44.1°, respectively, and (b) that the molecules are organized in rippled planes where they occur in relative antiparallel orientation linked together side by side by H bonds. This molecular organization of the tripeptide corresponds closely to that of an antiparallel α-pleated sheet, and likely constitutes the first example of a structure of this kind for which a characterization at the atomic level has been achieved. A molecular dynamics study has shown that the molecular conformation of the tripeptide in the crystalline state is determined primarily by intermolecular interactions. © 1994 John Wiley & Sons, Inc.
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360341103
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  • 135
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    Dynamics and thermomechanical stability of DNA in solution (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1483-1493 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present an analysis of the response of native DNA solutions to well-defined elongational flow fields. At low strain rates the DNA duplex behaves as an expanded coil. It shows a noncritical coil-stretch transition, suggesting relatively little hysteresis of the relaxation time. On the other hand, the relaxation time is consistent with a nonfree draining coil. At higher strain rates we observe midpoint scission. This has been modeled very successfully as a thermomechanically activated process. Scission occurs at hydrolyzable weak linkages along the constituent strands. Complete scission of the DNA helix is, however, considerably less prevalent than would be expected given the low stability of the constituent strands. We speculate upon the molecular origin and biological consequences of this enhanced stability. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360341106
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    β-Alanine containing cyclic peptides with predetermined turned structure. VPrevious parts of this series are in Refs. 15-18. (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1505-1515 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present paper we describe the synthesis, purification, single crystal x-ray analysis, and solution structural characterization by nmr spectroscopy, combined with restrained molecular dynamic simulations, of the cyclic hexapeptide cyclo-(Pro-Phe-β-Ala-Phe-Phe-β-Ala). The peptide was synthesized by classical solution methods and the cyclization of the free hexapeptide was accomplished in good yields in diluted methylenechloride solution using N, N-dicyclohexyl-carbodiimide. The compound crystallizes in the monoclinic space group P21 from methanol/ethyl acetate. The molecule adopts in the solid state a conformation characterized by cis β-Ala6-Pro1 peptide bond. The α-amino acid residues are at the corner positions of turned structures. The Pro1-Phe2 segment is incorporated in a pseudo type I β-turn, while Phe4-Phe5 is in a typical type I β-turn. Assignment of all 1H and 13C resonances was achieved by homo- and heteronuclear two-dimensional techniques in dimethylsulfoxide (DMSO) solutions. The conformational analysis was based on inter-proton distances derived from rotating frame nuclear Overhauser effect spectroscopy spectra and homonuclear coupling constants. Restrained molecular dynamic simulation in vacuo was also performed to built refined molecular models. The molecule is present in DMSO solution as two slowly interconverting conformers, characterized by a cis-tran isomerism around the β-Ala6-Pro1 peptide bond. This work confirms our expectations on the low propensity of β-alanyl residues to be positioned at the corners of turned structure. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360341108
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    Kinked structures of isolated nicotinic receptor M2 helices: A molecular dynamics study (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 1647-1657 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pore-lining M2 helix of the nicotinic acetylcholine receptor exhibits a pronounced kink when the corresponding ion channel is in a closed conformation [N. Unwin (1993) Journal of Molecular Biology, Vol. 229, pp. 1101-1124]. We have performed molecular dynamics simulations of isolated 22-residue M2 helices in order to identify a possible molecular origin of this kink. In order to sample a wide range of conformational space, a simulated annealing protocol was used to generate five initial M2 helix structures, each of which was subsequently used as the basis of 300 ps MD simulations. Two helix sequences (M2α and M2δ) were studied in this manner, resulting in a total often 300 ps trajectories. Kinked helices present in the trajectories were identified and energy minimized to yield a total of five different stable kinked structures. For comparison, a similar molecular dynamics simulation of a Leu23 helix yielded no stable kinked structures. In four of the five kinked helices, the kink was stabilized by H bonds between the helix backbone and polar side-chain atoms. Comparison with data from the literature on site-directed mutagenesis of M2 residues suggests that such polar side-chain to main-chain H bonds may also contribute to kinking of M2 helices in the intact channel protein. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360341209
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    Computer simulation of the free energy of peptides with the local states method: Analogues of gonadotropin releasing hormone in the random coil and stable states (1994)
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 815-839 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Helmholtz free energy F (rather than the energy) is the correct criterion for stability; therefore, calculation of F is important for peptides and proteins that can populate a large number of metastable states. The local states (LS) method proposed by H. Meirovitch [(1977) Chemical Physics Letters, Vol. 45, p. 389] enables one to obtain upper and lower bounds of the conformational free energy, FB (b, l) and FA (b, l), respectively, from molecular dynamics (MD) or Monte Carlo samples. The correlation parameter b is the number of consecutive dihedral or valence angles along the chain that are taken into account explicitly. The continuum angles are approximated by a discretization parameter l; the larger are b and l, the better the approximations; while FA can be estimated efficiently, it is more difficult to estimate FB. The method is further developed here by applying it to MD trajectories of a relatively large molecule (188 atoms), the potent “Asp4-Dpr10” antagonist [cyclo(4/10)-(Ac-Δ3Pro1-D-pFPhe2-D-Trp3-Asp4-Tyr-5-D-Nal6-Leu7-Arg8-Pro9-Dpr10-NH2)] of gonadotropin releasing hormone (GnRH). The molecule was simulated in vacuo at T = 300 K in two conformational states, previously investigated [J. Rizo et al. Journal of the American Chemical Society, (1992) Vol. 114, p. 2860], which differ by the orientation of the N-terminal tail, above (tail up, TU) and below (tail down. TD) the cyclic heptapeptide ring. As in previous applications of the LS method, we have found the following: (1) While FA is a crude approximation for the correct F, results for the difference, ΔFA = FA(TD) - FA(TU) converge rapidly to 5.6(1) kcal/mole as the approximation is improved (i.e., as b and l are increased), which suggests that this is the correct value for ΔF; therefore TD is more stable than TU. (The corresponding difference in entrophy. TΔSA = 1.3(2) kcal/mole, is equal to the value obtained by the harmonic approximation.) (2) The lowest approximation, which has the minimal number of local states, i.e., based on b = 0 (no correlations) and l = 1 (the angle values are distributed homogeneously), also leads to the correct value of ΔF, within the error bars. This is important since the lowest approximation can be applied even to large proteins. (3) The method enables one to define the entropy of a part of the molecule and thus to measure the flexibility of this part. We have verified that the results for T[SA(TU) - SA(TD)] of the tail alone converged to 2.4(1) kcal/mole, which demonstrates the relatively high flexibility of the tail in the TU state. In order to study the random coil state, the Asp4-Dpr10 analogue and its linear version were simulated by MU at 1000 K. We have been able to calculate a lower bound, ∼ 25 kcal/mole for T[S(linear) - S(cyclic)], which is the reduction in the conformational entropy caused by the ring closure. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360340703
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340105
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340106
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340111
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340202
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340206
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    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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    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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    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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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340303
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340309
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340308
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    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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    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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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340405
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    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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  • 154
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    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.
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    URL: http://dx.doi.org/10.1002/pen.760340409
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    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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    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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    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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  • 158
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    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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  • 159
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    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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  • 160
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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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    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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  • 162
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    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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    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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  • 164
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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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    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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  • 166
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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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  • 167
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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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    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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    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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    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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  • 171
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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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    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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  • 173
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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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    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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  • 175
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    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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  • 176
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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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  • 177
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    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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  • 178
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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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  • 179
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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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  • 180
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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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  • 181
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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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  • 182
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    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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  • 183
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    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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  • 184
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    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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  • 185
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    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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  • 186
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    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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  • 187
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    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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  • 188
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    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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  • 189
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    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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  • 190
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    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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  • 191
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    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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  • 192
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    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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  • 193
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    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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  • 194
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    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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  • 195
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    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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  • 196
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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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  • 197
    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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  • 198
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    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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  • 199
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    Electronic Resource
    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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  • 200
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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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