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  • 1987  (606)
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  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1021-1034 
    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: Equations are derived that relate the orientation of “pseudo-affine” reoriented structural units after a biaxial deformation to the degrees and the directions of the effective drawings. The connection between these drawing parameters and those externally applied is analyzed in detail. It is shown how a comparison of these two sets of drawing parameters allows conclusions regarding the distribution throughout the material of the stresses that cause the deformation, the inhomogeneity of the deformation, and the role of non-orienting flow during deformation. In particular, the orientation of biaxially drawn poly(ethylene terephthalate) films is investigated, and it is shown what general information can be obtained on the deformation behavior of this material on the basis of these considerations.
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1059-1068 
    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: Scale-up from small laboratory size extruders to large production size extruders is a procedure of great practical importance. Many scale-up rules and theories have been proposed in the past, however it is not always clear how the different scale-up methods will affect extruder performance. A basic analysis of scale-up in plasticating single screw extruders is developed from which the effect of a certain scale-up strategy on extrusion performance can be evaluated in terms of solids conveying, melting, melt conveying, mixing, residence time, heat transfer, power consumption, and specific energy consumption. Various existing scale-up theories are evaluated and compared using the basic analysis. A number of existing scale-up theories have some significant drawbacks, in particular with non-constant specific energy consumption and imbalance between melting rate and pumping rate. Conditions that are desirable to achieve in scale-up are enumerated and ranked in terms of importance. This leads to two new scale-up methods that result in constant mechanical specific energy consumption and high throughput rates. The first scale-up method keeps the specific surface area constant. This scale-up should work well for high values of the Brinkman number. However, at low values of the Brinkman number, the melting rate may be insufficient. The second scale-up method keeps the melting rate at low Brinkman number equal to the pumping rate and, thus, should be useful in cases where the first scale-up method cannot be used.
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 4
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1128-1136 
    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 plane strain fracture toughness and fracture mechanisms of several tough engineering plastics have been studied and compared with poly(methyl methacrylate) (PMMA), a relatively brittle polymer. The tough polymers all are observed to form a multiple craze zone at the crack tip, which is shown to be the primary source of plane strain fracture toughness in these materials. The multiple craze zone is retained during slow crack growth but is metastable, and at a critical stress intensity and associated crack velocity, the system passes through a transition to a greatly accelerated single craze mode of unstable propagation.
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  • 5
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1148-1155 
    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 optical properties of bisphenol-A polycarbonate resin as described by the complex index of refraction, N = n - ik, are derived by Kramers-Kronig analysis of experimental absorption and reflectance data obtained in the range 40μm ≥ λ ≥ 105 nm. Electronic absorption processes in polycarbonate are characterized by two broad absorption peaks centered at ∼200 and ∼100 nm.
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  • 6
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1182-1186 
    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: Three-layer coextruded blown (either blend or composite) films, made of low-density polyethylene and linear lowdensity polyethylene (1:1 ratio) of identical density, were compared. The tensile properties of both systems are nearly as high as those of the linear polyethylene while high strain rate properties including impact strength and tear resistance of the composite film are superior. Some structural insight was obtained by thermal analysis and thermoelastic measurements. Structure property relationships are discussed in light of the unique behavior, structure, and morphology of linear low-density polyethylene. The two polyethylenes are only compatible to a rather limited extent mainly affecting their blend behavior. However, a strong mutual reinforcement effect was observed.
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  • 7
    Electronic Resource
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1203-1208 
    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 Viton copolymer containing vinylidene fluoride (VF2) and hexafluoropropylene (HFP), and a terpolymer containing VF2, HFP, and tetrafluoroethylene (TFE) were cross linked using varying amounts of Bisphenol AF to yield two series of fluoroelastomer networks, Stress-strain isotherms in elongation were determined for these samples at several temperatures and at two degrees of swelling with phenyl acetate. Strain-induced crystallization was observed, as evidenced by upturns in the isotherms at high elongations. It appears to be more pronounced in the terpolymer samples, presumably because the TFE units not only can crystallize themselves, but can co-crystallize with the VF2 units. The crystallization was found to persist upon moderate increase in temperature, but was suppressed when the networks were swollen, Thermoelastic (force-temperature) measurements were used to obtain values of the fraction fe/f of the elastic force that is due to energetic effects. Negative values were obtained for both types of samples and, in the case of two samples studied in detail, their magnitudes increased with increase in elongation. The magnitudes were larger and the increases more pronounced in the case of the terpolymer networks, as would be expected from a greater tendency for straininduced crystallization.
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  • 8
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1221-1228 
    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 transesterification reaction of molten ethylene and vinyl alcohol copolymers (EVA), in presence of paraffinic alcohols and basic catalysts, leads to high conversion of the ester groups to secondary alcohol in both discontinuous and continuous processing equipment. Various kinds of alcohols and two different catalysts were used. Sodium methoxide is a powerful catalyst for the equilibrated transesterification reaction, but we also observed side reactions, such as cross-linking with low-molecular-weight alcohols and hydrolysis of the catalyst followed by partial saponification of the EVA. Kinetic studies were performed in the presence of dibutyltin dilaurate, an efficient catalyst without any side reactions. The solubility of the main alcohol reagents was verified by diffusion measurements. The general reaction scheme and the related kinetics, corresponding to a homogeneous system, lead to a fair evaluation of the rate constants.
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  • 9
    Electronic Resource
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1252-1257 
    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 mechanical properties of polyurethane-unsaturated polyester interpenetrating polymer networks (IPNs) that were prepared by reaction injection molding (RIM) process were measured with variations In composition, cross-link density, and relative reaction rate. From dynamic mechanical analysis (DMA), it was found that the two component polymers had a good compatibility over the whole composition range. The tensile strengths of the blends were greater than those of the pure components and had a maximum value at 50/50 composition. The modulus of elasticity and surface hardness decreased and the impact strength increased as the polyurethane content was increased, but the changes were not high at low polyurethane content, below 50%. For higher cross-link density, the compatibility was enhanced and the mechanical properties were improved. When the reaction rates of the components were different, some extent of phase separation was found in DMA and the properties were affected adversely.
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  • 10
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1448-1460 
    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 used to predict the behavior of the support/catalyst/polymer macroparticle during the gas phase polymerization of propylene. The problem is focused on the micrograin level of the macroparticle, and the emphasis placed on the combined reaction and diffusion processes taking place in the micropartiele. Particular attention is given to the effect of the main geometry parameter, the size of the catalytic nucleus, on polymerization variables. Fragmentation rate, monomer concentration, and temperature are studied in terms of their dependence on the geometry-related dimensionless numbers typical of the process. A strong influence of the micrograin size on the commanding process variables is predicted by the model. Fragmentation proves relevant to the overall process and critical to define the time scale of temperature excursions. Micrograin nucleus size are found to be important when computing both maximum temperatures and minimum yields. The model suggests criteria for predicting “a priori” the combination of reaction parameters that will produce a diffusion-limited reaction regime in the microparticle.
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  • 11
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1481-1481 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 12
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1504-1511 
    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: Blending of a poly(ether urethane) with a polyphosphonate obtained by phase transfer catalyzed polycondensation of 4,4′-biphenol and chloromethylphosphonic dichloride generates a phase-separated material. One phase contains the soft segment of the polyurethane. This has been excluded from a high-Tg phase that contains ionic species formed mainly by proton transfer and elimination reactions between the hard segment of the polyurethane and the polyphosphonate. Two glass transitions appear in the blend: one close to the Tg of the polyphosphonate and one belonging to the excluded soft segment of the polyurethane. The low temperature Tg decreases with the increasing content of the polyphosphonate, whereas the high temperature transition increases slightly, indicating an increasing purity of the soft segment and the presence of ionic interactions in the hard segment. The presence of ionic interactions is confirmed by NMR analysis of the blend. Comparison of the spectra of the blends with those of the pure components, along with two-dimensional experiments, indicate a reaction involving the chloromethyl groups of the polyphosphonate and the nitrogens of the polyurethane.
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  • 13
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1530-1541 
    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: Blends of polycarbonate (PC) and poly(hexamethylene sebacate) (HMS) with two different molecular weights were prepared and their thermal properties were studied via differential scanning calorimetry. It was found that the high molecular weight PC (HPC) and high molecular weight HMS (HHMS) were partially miscible as evidenced by the decrease in glass transition temperature of HPC in the blends. This partial miscibility is attributed to the interaction of the carbonyl dipole of the ester group and the highly polarizable aromatic carbonate structure. When the low molecular weight PC or HMS was used, the compatibility was enhanced because of the increased entropic contribution to the Gibbs free energy of mixing. In all the blends prepared, the PC crystallized as a result of the plasticizing effect of HMS. Bisphenol-A diphenyl carbonate (dimer) was synthesized and used as the dimeric model of PC. This material was found to be an excellent diluent for HPC. A single glass transition was found in the HPC/dimer system and the temperature was dependent on the composition. The Couchman's equation was found to fit very well the glass transition temperature versus composition relationship for this system. A single glass transition was also found in the HHMS/dimer system. The melting point depression analysis was performed and resulted in a very low heat of fusion for the 100% crystalline HHMS. It may suggest that the dimer and HHMS are not completely miscible in the amorphous region.
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  • 14
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1562-1571 
    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 temperature rising elution fractionation (TREF) technique makes use of the differential crystallizabilities, introduced by short chain branches (SCB), to fractionate polyethylenes (PE) on the basis of the SCB level of any one chain. This allows one to probe the SCB distribution of a polymer. The TREF technique has been applied to blends of PE by recognizing that the two commercial types of low density polyethylene, high pressure (HP-LDPE) and linear low density (LLDPE), have different short chain branching distributions. Other common copolymers of ethylene, like ethylene vinyl acetate (EVA) or terpolymers like ethylene/propylene/hexadiene (EPDM), also have different SCB types, levels, and distributions and therefore have different TREF behavior. We have constructed a TREF apparatus that can be used in a number of different types of blend studies. The first is an Analytical-TREF, which gives a profile of the amount of polymer with a given SCB level and can be used to quantify HP-LDPE/LLDPE blends. We have also modified the technique to construct a stop-flow TREF apparatus, which enables one to separate fractions on the basis of the branching levels. The fractions can then be analyzed by size exclusion chromatography, IR, 13C NMR, or DSC. The use of these TREF techniques to characterize blends of HP-LDPE/LLDPE, LLDPE/EVA, PE/EPDM, and PE/polyisobutylene is discussed.
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  • 15
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1601-1610 
    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 is described for the noncontact evaluation of structural morphology in polyblends by light scattering. Optical methods are attractive for the on-line characterization of translucent materials because they are noninvasive, rapid, and applicable to high temperature materials. One limitation of conventional light-scattering techniques is their requirement for relatively thin samples in order to avoid multiple-scattering effects that smear out the details of the light diffraction pattern. The approach described in this paper is meant to circumvent this limitation by resorting to turbidimetric measurements, which provide useful information on the average size, shape, concentration, and orientation of the dispersed phase particles even in the presence of multiple scattering. The sample thickness is no longer restricted, and methods are described by which the near-surface volume of infinitely thick parts may be inspected with access to a single side of the material. Results are presented for polypropylene-polycarbonate (PP/PC) samples of different thicknesses and microstructural morphology, including fibrillar-type oriented structures.
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  • 16
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1634-1641 
    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: Reactive polystyrene (OPS) and reactive polyethylene (CPE) with oxazoline and carboxylic acid functionality, respectively, were melt blended in a Rheomix mixer under a variety of conditions. The properties of these blends were examined and correlated with the compositions and mixing conditions such as shear rate, time, and temperature. An increase in torque was observed, which is believed related to chemical reaction between OPS and CPE. The difference between the maximum and minimum torque (Tmax-Tmin), increases from 48 to a maximum of 510 m-g for 10 and 40% CPE reacted blends, respectively, But on further increase in the CPE amount in the blend the torque increase drops reaching a final minimum value of 133 m-g for a blend with 90% CPE. Differential Scanning Calorimetry (DSC) studies reveal a single first order transition, due to CPE, for each of these polymer blends. Furthermore, evidence of the glass transition temperature for OPS diminishes with increasing CPE content and mixing time. Scanning Electron Micrographs (SEM) show a fine dispersion in these reactive blends, with particle size much smaller than a micron. Blends with 50% or more CPE have no distinguishable features as such. Mechanical properties such as elongation at break of reacted blends are improved over the nonreactive polyethylene (PE) and polystyrene (PS) blends. An intermolecular reaction between the OPS and CPE results in a graft polymer, which imparts improvement in the overall properties of these reacted blends. The maximum grafting reaction corresponds to 40% CPE blend, which is being evaluated as a potential compatibilizer.
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  • 17
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1657-1661 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of varying interaction parameters on the phase diagrams of ternary polymer blends was explored by simulating spinodals through use of the Flory-Huggins lattice theory. Results indicate that miscibility is favored for the case of ternary mixtures of marginally miscible or marginally immiscible pairs where all pair interactions are nearly athermal. Miscibility is restricted for asymmetric ternary blends when one of the polymer pairs is either strongly miscible or strongly immiscible. For symmetric blends of partially immiscible pairs, both two-phase and three-phase miscibility gaps are predicted.
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  • 18
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1675-1680 
    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: Sheets of medium density polyethylene (MDPE) were extruded through a slit die containing an internal separator. Thus, the melt stream was momentarily split before emerging from the die. A line of separation was evident in the extruded sheets. It is attributed to incomplete welding or healing. Measurements of tear energy Gc revealed that the extruded sheets were anisotropic and that the weld line was extremely weak after extrusion start-up, only about 1/5 of the strength elsewhere. As extrusion continued, the strength of the weld line increased to reach that of the bulk material after about 10 min. This is attributed to an increasing temperature of the melt in the die region, aiding interdiffusion. A sample containing 30% by weight of short glass fibers showed less initial weld-line weakness but the weld line remained weak in this case, even after long extrusion times.
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  • 19
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1703-1712 
    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 semi batch reactor was developed to investigate the oligomerization reactions in the melt transesterification of dimethyl terephthalate with ethylene glycol catalyzed by metal acetate catalyst. The detailed kinetic scheme based on the molecular species model is used to estimate the conversion of methyl ester groups and the concentrations of various oligomeric species. The numerical simulation of the model shows that the oligomerization reactions lower the overall conversion of methyl ester end groups. Effects of ethylene glycol/dimethyl terephthalate mole ratios, reaction temperature and, catalyst concentration on the conversion, oligomer concentration, oligomer molecular weight, and molecular weight distribution were also analyzed.
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  • 20
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    Polymer Engineering and Science 27 (1987), S. 703-715 
    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 series of copolymers containing styrene and a fluorocarbinol substituted styrene, vinyl benzyl hexafluorodimethyl carbinol, were prepared by substitution of hexafluoroacetone on polystyrene followed by hydrolysis, and by copolymerization of styrene and substituted styrene monomers. Sorption of dimethyl methyl phosphonate, DMMP, vapor in the copolymers was examined at 135°C by the piezoelectric sorption method and at 135 to 165°C by Inverse Gas Chromatography, IGC, and the results were analyzed by the Flory-Huggins equation. Both methods yield similar negative values of the Flory-Huggins Chi parameter at 135°C, and the Chi values are observed to become increasingly negative to -4.9 as the percent substitution of the aromatic rings In the copolymer is increased to 54 mole percent. A simplified thermodynamic analysis, based on experimental studies of the hydrogen bond formed between DMMP and hexafluoro-isopropanol, an analog of the fluoro-carbinol, through infrared spectroscopy and calorimetry at ambient conditions, is shown to predict the Chi dependency on copolymer composition observed at 135°C to within the accuracy of the experimental observations, however, the analysis predicts a decrease in Chi with increasing temperature that is too high relative to values observed by IGC at temperatures greater than 135°C.
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  • 21
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    Polymer Engineering and Science 27 (1987), S. 753-763 
    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 role of segmental diffusion in step-growth polymerizations has been studied using a simple, phenomenological theory. Theoretical results have been generated to study the effect of the parameters, several of which can be estimated from experiments on non-reacting systems. The values of the parameters have been selected in this study in such a manner that segmental-diffusional limitations are encountered quite early during polymerization. This facilitates detailed parametric sensitivity studies. Thereafter, the model is used to predict behavior of trains of reactors, and more appropriate values are used for the parameters. Segmental-diffusional limitations are then limited to final stages of polymerization (as indeed they are in industrial practice).
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  • 22
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    Polymer Engineering and Science 27 (1987), S. 773-780 
    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: Glassy polycarbonate specimens with different degrees of aging were tested in puncture for the purpose of determining the ductile/brittle transition temperature in biaxial tension. The results show that increasing amounts of aging increase the transition temperature from -95 to -70°C. All transitions appear too low In temperature. This was confirmed by using strip-biaxial specimens that become brittle at a significantly higher temperature. In addition to this problem, the load deflection curve also can lead to an overestimation of the load and energy to initiate cracking. A finite element model of the puncture test suggests that the compressive stress under the dart may have shifted the onset of brittleness to much lower temperatures.
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  • 23
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    Polymer Engineering and Science 27 (1987), S. 816-822 
    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 is concerned with the effect of thermal history on the rheology of three liquid crystal copolymers. The polymers were heated to temperatures above their melting points and then cooled down. During the cooling cycle, the dynamic mechanical properties were monitored. It was found that these properties remained unchanged at temperatures as low as 30°C below the normal melting points for two copolyesters of 60 mole percent p-hydroxybenzoic acid (PHB) and 40 mole percent poly(ethylene terephthalate) (PET) (60-40 PHB/PET) and 80 mole percent PHB and 20 mole percent PET (80-20 PHB/PET). For a copolymer of PHB and 2,6-dihydroxynaphthaic acid, there was a gradual increase in the properties with decreasing temperature. However, at a critical temperature all three systems exhibit a sudden increase In dynamic mechanical properties. The kinetics of solidification were also monitored, and it was found that at temperatures well below the melting point, it took 4 to 6 min before the solidification process impeded flow. Extrusion studies on these materials were also carried out, and it was observed that in this supercooled state, the polymers exhibited significant die swell. The samples also exhibited a fibrous texture and were more oriented than when extruded isothermally above the melting point.
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    Polymer Engineering and Science 27 (1987), S. 837-841 
    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 mutual diffusion coefficients for three molten polystyrene(PS)-hydrocarbon systems - PS-in-xylene, PS-n-octane, and PS-n-nonane - were measured by using a sorption apparatus with quartz spring in the temperature region from 130 to 175°C and for mass fraction of hydrocarbon ranging from 0 to 0.15. The mutual diffusion coefficients were correlated with good agreement by the freevolume theory.
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    Polymer Engineering and Science 27 (1987), S. 857-860 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polymer blends of an amorphous polyamide with poly(2vinyl pyridine) (P2VP) are presented. Differential scanning calorimetry results suggest that the system exists as a single phase material as evidenced by a single glass transition temperature. However, as illustrated by light scattering studies, this miscible binary mixture possesses a relatively low, lower critical solution temperature (LCST). Fourier transform infrared (FTIR) spectroscopic investigations indicate that the interactions occur in the blend between the N—H group of the polyamide and the —N: atom of P2VP and that the strength of the Interactions between the components is nearly identical to that occurring in the self-association of the pure amorphous polyamide. Additionally, by monitoring the concentration of “free” carbonyl groups, a quantitative measure of the number of interactions occurring in the blend is obtained.
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  • 26
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    Polymer Engineering and Science 27 (1987), S. 876-886 
    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 deformation of biaxially oriented polypropylene sheet produced by the BeXor process has been examined in terms of the hierarchical solid state structure described previously. The mechanical properties have been examined over a range of temperatures and strain rates. The anisotropic nature of uniaxial tensile deformation was analyzed from simultaneous measurements of longitudinal extension and lateral contraction in the width and thickness directions, by determining the shape of uniaxially deformed spherulites, and by examining fracture surfaces in the scanning electron microscope (SEM). It was determined that deformation proceeds by elastic extension of the amorphous network and plastic shear deformation of the crystalline regions in the plane of the sheet, and in the thickness dimension, by voiding with induced fibrillation. It is suggested that the property improvements, particularly at low temperatures and high strain rates, which are achieved by the BeXor process, result from changes in the hierarchical structure at the size scale of the crystalline lamellae. Specifically it appears that the small crystalline blocks formed by breakup and recrystallization of lamellae are more easily deformed than the original large coherent lamellae.
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  • 27
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 27 (1987), S. 939-944 
    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: Multitechnique surface characterization of plasma and chemically modified poly(methyl methacrylate) (PMMA) is reported using Low Energy Ion Scattering Spectrometry (LEIS or ISS) and angular-dependent X-Ray Photoelectron Spectroscopy (XPS or ESCA). A complete picture of the depth, extent, and mechanism of modifications developed. ISS yields results, which especially complement ESCA because of the sensitivity to functional group arrangement due to shadowing and shielding of atoms in the topmost layer.
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    Polymer Engineering and Science 27 (1987), S. 964-975 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental study was conducted to investigate the effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin during isothermal cure. For the study a general-purpose unsaturated polyester resin was cured in the presence of t-butyl perbenzoate as Initiator. The curing behavior of the resin was investigated using differential scanning calorimetry (DSC). Three different thermoplastic low-profile additives were used, namely poly(vinyl acetate) (PVAc), poly(styrene-co-butadiene), which is also known as KRATON DX-1300, and dehydrochlorinated Isobutylene/isoprene copolymer, often referred to as conjugated diene butyl (CDB) rubber. Each of the these additives, about 30 weight percent, was first dissolved in styrene. The solution was then mixed with unsaturated polyester resin and CaCO3. The CaCO3 particles helped stabilize the emulsions consisting of resin and KRATCN, and of resin and CDB. For each resin formulation, a series of isothermal DSC runs were made at various levels of cure pressure. It was found that for all three low-profile resins investigated, the final degree of cure went through a maximum as cure pressure was increased from atmospheric to 6.21 MPa (900 psi). We have observed evidence that in the presence of an initiator generating free radicals, the unsaturated double bonds in the KRATON and CDB undergo grafting reactions with the styrene monomers and unsaturated polyester resin, increasing the glass transition temperature of KRATON and CDB, to an extent which varies with the cure conditions employed. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer. The rheological measurements indicate that the resin/CaCO3/KRATON and resin/CaCO3/CDB systems give rise to gel times shorter than the resin/CaCO3/PVAc system. It is concluded that both KRATON and CDB are more effective, both for enhancing the rate of cure of unsaturated polyester resin and imparting impact properties to the cured composites, than those thermoplastic low-profile additives that contain neither unsaturated double bonds nor a chemical structure that has rubber-like properties in the solid state.
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 27 (1987), S. 1275-1283 
    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: Multiordering parameter models have been quite successful in rationalizing volume and enthalpy behavior of glasses subjected to various thermal histories in the glass transition range and even at lower temperatures. In the past we suggested a generalization of such models to encompass what is now termed physical aging, i.e., recovery as monitored by mechanical experiments such as creep and stress relaxation. Our initial investigation indicated qualitative agreement between the generalized model and experimental behavior. We have now more completely investigated this area and found a convenient approximation through which behavior can be calculated in most situations without using a distribution of mechanical relaxation or retardation times. Using this technique, we find that essentially quantitative agreement between this model and experimental results is possible only when a very sharp distribution of volumetric recovery times, like that of a single ordering parameter model, is used, Broader distribution functions result in aging behavior which is much more sluggish than observed experimentally. This result is particularly disturbing since such sharp distribution functions have been shown to be incompatible with direct observations of volume recovery.
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    Polymer Engineering and Science 27 (1987), S. 1317-1322 
    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 fractional-life method coupled with dynamic differential scanning calorimetry (DSC) scan was employed to study the kinetics of the isothermal polymerization of the DGEBA (diglycidyl ether bisphenol A)/HHPA (hexahydrophthalic anhydride)/BDMA (benzyl dimethyl amine) resin system. This method avoids the problem of uncertainty in the total heat evolution in the isothermal DSC scan, The reaction orders obtained for this epoxy resin vary from 1.05 to 1.44 in the temperature range 118-135°C and are believed to be more accurate than those determined in previous studies.
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    Polymer Engineering and Science 27 (1987), S. 1334-1337 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The chain orientation, induced by hot drawing, decreases the sorption capacity of polystyrene due to the tighter packing of macromolecules in the oriented material. Density measurements and decay of birefringence indicate that the loss of orientation Is a much more rapid phenomenon than the thermal shrinkage of the polymer.
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    Polymer Engineering and Science 27 (1987), S. 1345-1357 
    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 reviews control strategies employed in the injection-molding process. For clarity, the controlled variables have been categorized into all-phase control, phase-dependent control, and cycle-to-cycle control. All-phase control includes variables that must be monitored and controlled at all times; i.e., in all the phases. Control of variables that are triggered during a specific phase are discussed under phase-dependent control. In cycle-to-cycle control, previous data are used to predict future trends and take appropriate corrective actions, The cyclic, dynamic, and unsteady state nature of the injection-molding process is discussed with respect to the conventional proportional-integral (PI) and proportional- integral-derivative (PID) controllers as well as the more advanced control schemes such as self-tuning control, optimal control, and statistical process control. Suggestions involving specific advanced control schemes and recommendations for future research in injection-molding process control also are made.
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    Polymer Engineering and Science 27 (1987), S. 1386-1389 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Investigation of the performance of a large-diameter conventional motionless mixer used as a continuous reactor for styrene polymerization showed that it behaved adiabatically. Computer simulation (in which the mixer is treated as an ideal plug-flow reactor having perfect radial mixing) predicts this tendency in terms of axial temperature profile. To avoid adiabatic polymerization, with its attendant problems of plant operability and polymer quality, the use of motionless mixers having internal heat transfer surface is indicated.
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    Polymer Engineering and Science 27 (1987), S. 1411-1418 
    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 modification of the injection-molding machine, incorporating additional filters, an accumulator, and a servovalve, was shown to reduce the peak cavity pressure variations, in as much as the variations using the microprocessor system were random in comparison to the variations using the normal mode of operation, which exhibited nonstationarity and autoregressive behavior. If the peak hydraulic pressure could be randomized, then the peak cavity pressure variations also would be random. No closed-loop control would be needed to control the peak cavity pressure.
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    Polymer Engineering and Science 27 (1987), S. 25-32 
    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: Ultrasonic fractography studies were performed on poly(methyl methacrylate) of high molecular weight. The transient fracture velocity change at the slow-to-fast transition during discontinuous propagation has been measured precisely. Fast fracture starts with a characteristic velocity which falls in a narrow range between 90 to 150 m/s, nearly independent of the loading speeds and the specimen temperature from -50 to 40°C. Parallel double-cantilever-beam specimens exhibited stick-slip type propagation whose velocity change was also evaluated. In these specimens, the fast fracture abruptly slows down to speeds on the order of 10° m/s. These intermediate velocities have never been obtained in the slow-to-fast transition. Velocity measurements under hydrostatic pressure have shown that fracture velocities decrease significantly with increasing pressure, and that the slow-to-fast transition tends to disappear at a pressure between 5 and 10 MPa. Models have been presented concerning the mechanism of the slow-to-fast transition, crazing and cracking under superposed cyclic stress field, and the relationship between dynamic toughness and fracture velocity in this material.
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    Polymer Engineering and Science 27 (1987), S. 41-45 
    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 development of plastic deformation and crazing in the neighborhood of a notch has been studied in connection with nonlinear fracture processes of crystalline ductile polymers, polyethylene, polypropylene, and propylene-ethylene block copolymers. After revealing the morphology of plastic deformation around the notch and studying the effects of crystalline structure on ductile fracture processes, the J-energy analysis was applied to give a criterion for crack initiation in the fracture of these elastic-plastic materials. The material resistance to stable and unstable cracking was characterized using the curves of J against crack extension Δα.
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    Polymer Engineering and Science 27 (1987), S. 82-85 
    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: Correlations of the stress intensity factor, KI, with crack speed, ċ, have been obtained in a number of detergent solutions each having different detergent concentration. A constant crack speed region was observed in high density polyethylene. The KI independent constant crack speed was found to vary linearly with detergent concentration. The viscosity of the detergent solution increases with concentration and hence this region is not controlled by the hydrodynamic properties of the environment in contrast with Williams' model. The KI-ċ data were compared with existing models of crack propagation.
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    Polymer Engineering and Science 27 (1987), S. 109-109 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 27 (1987), S. 116-123 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fiber reinforced plastics offer many structural advantages for a variety of designs. Before these material systems can achieve more widespread usage, however, some of the unanswered questions regarding the long-term behavior and durability of these materials must be answered. Nonlinear compliance data is presented for T300/934 and T300/5208 graphite/epoxy composites. Several nonlinear viscoelastic techniques are compared for modeling the response. Comments for applying nonlinear models to orthotropic materials are given. A procedure for predicting long term laminate response from short term unidirectional data is reviewed.
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    Polymer Engineering and Science 27 (1987), S. 131-140 
    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 studied the failure of a urethane elastomer due to cyclic compressive loading, using loading frequencies and specimen sizes for which internal heat generation is an important factor. The eventual failures were generally manifest by internal cracks growing transverse to the loading direction. A variety of experimental analyses indicate that this failure is primarily thermal, in that the temperature rise due to viscous dissipation eventually leads to a melting of the hard segment domains which act to reinforce the material. No strong indication of thermal or thermomechanical bond scission was obtained, although a progressive reduction in the rubbery modulus was noted.
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    Polymer Engineering and Science 27 (1987), S. 144-148 
    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 the linear viscoelastic range the long term behavior of viscoelastic materials - such as polymers - can be described by using exponential series with a limited number of terms for the approximation of the relaxation modulus or of the creep compliance. This procedure can be extended to the nonlinear viscoelastic range by multiplying the linear parameters of the material by certain nonlinearity factors, which depend upon the level of the applied loading. Application of this method to stress relaxation data of several polymers has shown that nonlinearity factors can be approximated as linear functions of the applied constant strain. From creep tests, on the other hand, one can observe that the immediate strain response to the suddenly applied stress is linear elastic even in the nonlinear viscoelastic range of the investigated polymer. The computation of the linear viscoelastic material parameters as well as of the nonlinearity factors is conducted numerically by using least squares techniques. Good agreement between computed results and experimental data can be observed in the presented examples.
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    Polymer Engineering and Science 27 (1987), S. 225-231 
    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: Multilayer composite films consisting of polyolefins, either polypropylene, linear low density or medium density polyethylene, a thin adhesive layer, and a polyamide in various ratios were prepared using two basically different processes. The first, a conventional blown film process in which the extrudate is stretched while in the molten state; and the second, a two-stage process in which the quenched extrudate is stretched at a temperature below the polymers' melting point. The films so prepared, having identical composition and similar extents of stretching, were compared on the basis of their tensile properties, thermoelastic shrinkage, oxygen transmission rate, and thermal behavior. The effects of stretching temperature, rate, and extent on the behavior of the composite films and control single layer films were investigated. The stretching temperature was found to be the dominating single process parameter in determining the films' behavior. The overall performance including tensile properties, barrier, and shrink properties of the “cold” stretched films was found markedly superior to that of the conventionally blown films. The stretched composite films possess physical properties that cannot be attained by the conventional process.
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    Polymer Engineering and Science 27 (1987), S. 367-379 
    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 steady state and dynamic shear behavior of eleven commercial linear low density polyethylenes (LLDPE) and one low density polyethylene (LDPE) resin were measured in capillary and parallel plate geometries at T = 150 to 230°C. The extrudate swell and the Bagley correction were determined. A large pressure effect on capillary flow of narrow molecular weight distribution LLDPE was observed and a new corrective procedure was proposed. After the correction the steady state viscosity was found to be equal to the dynamic (not complex) viscosity: η(\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}) = η'(ω = \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}). A newly proposed four parameter relation between η and the deformation rate was found to provide a simple means for computation of the zero shear viscosity, ηo, and the primary relaxation time. Both these parameters showed a high degree of correlation. The expected relation: ηo ∝ Mw3.4 was observed for low molecular weight samples with low polydispersity. The LLDPE activation energy of flow, Eσ=29.9 ± 1.8 kJ/mole, was determined.
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    Polymer Engineering and Science 27 (1987), S. 380-386 
    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 uniaxial extensional flow at 150°C of 11 linear low density polyethylenes (LLDPE) and one low density polyethylene was measured in a Rheometrics Extensional Rheometer. The presence of silicone oil did not affect the results. However, large effects of the molding time were observed. For specimens molded for 14 min, strain hardening was not observed for any gas-phase polymerized LLDPE. As the molding time was increased to 40 min, the strain hardening was quite apparent, the elongational viscosity nearly doubled, the equilibrium plateau vanished, and the maximum strain at break Increased by about 20 percent. Explanation for the molding time effects can be found in the concept of low entanglement density in the virgin gas-phase resins. The entanglement increases with time at temperatures above the melting point. The specimens molded for longer time show strain hardening.
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    Polymer Engineering and Science 27 (1987), S. 440-450 
    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 compatibility of polymer blends of high-molecular-weight polycarbonate (PC) and high-molecular-weight poly(hexamethylene sebacate) (HMS) were characterized. Samples were prepared by solution blending them In methylene chloride followed by doctor blade casting. Optical spectroscopy, tensile stress-strain, differential scanning calorimetry, and dielectric relaxation spectroscopy were employed to determine the physical and mechanical properties of the blends. These high-molecular-weight blends exhibit a limited solubility of HMS In PC as evidenced by a decrease in the glass-transition temperature of PC. In fact, HMS solubility increases PC mobility sufficiently to allow partial crystallization of PC. Over most of the composition range, HMS phase separates and crystallizes.
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 463-469 
    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: Styrene/butyl acrylate copolymers with layer morphology were synthesized using an emulsion copolymerization process, The kinetic parameters studied include monomers composition, initiator and transfer agent content, feeding time, and monomer addition sequence. The final product consists of a homopolymer nucleus surrounded by concentric shells of copolymers with different composition; the initial composition is quite rich in the monomer that forms the nucleus while the process ends with an enriched layer of the second homopolymer. Since the middle copolymer layer tends to increase the compatibility among the original homopolyers, we expected to have a set of core-shell products with completely different properties. However, the experimental results showed that this was not the case. The composition effect on the viscoelastic properties shows, on one hand, that an increase in the butyl acrylate content lowers the elastic response of the final product, and on the other hand, that the elasticity increases with copolymer content. As the initiator content in the reaction media increases, the viscosity of the coreshell products decreases because of the existence of a media flooded with free radicals. If the butyl acrylate is first added, a graft polymerization is favored because of the polar nature of this homopolymer and, therefore, the molecular weight level increases.
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    Polymer Engineering and Science 27 (1987), S. 500-503 
    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: Microcellular polymer foams exhibit greatly improved mechanical properties as compared to standard foams due to the formers' small bubble size. Microcellular foams have bubbles with diameters on the order of 10 microns, volume reductions of 30 to 40 percent, and six or seven times the impact strength of solid parts. They are produced through the use of thermodynamic instabilities without the use of foaming agents. This method leads to a very uniform cell size throughout a part's cross section. A theoretical model for the nucleation of microcellular foams in thermoplastic polymers has been developed and experimentally confirmed. This model explains the effect of various additives and processing conditions on the number of bubbles nucleated. At levels of secondary constituents below their solubility limits, an increase in the concentration of the additive or the concentration of gas in solution with the polymer increases the number of bubbles nucleated. Nucleation in this region is homogeneous. Above the solubility limit of additives, nucleation is heterogeneous and takes place at the interface between second phase inclusions and the polymer. The number of bubbles nucleated is dependent on the concentration of heterogeneous nucleation sites and their relative effect on the activation energy barrier to nucleation. In the vicinity of the solubility limit, the two mechanisms compete.
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    Polymer Engineering and Science 27 (1987), S. 518-523 
    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 process described as “roll-drawing” has been applied to commercial extruded sheets of isotactic polypropylene (M̄n = 70,900). Preheated billets were drawn into thin, clear, transparent sheets in a single pass, producing uniaxial orientation of the polymer molecules in the draw direction. At the maximum draw ratio of 20, the ultimate tensile strength and Young's modulus in the draw direction were 0.5 GPa and 20 GPa respectively. The mechanical properties transverse to the draw direction were virtually unchanged. The theory of fiber reinforcement for unidirectional anisotropic plates was applied to interpret the orientation dependence of the stress-strain behavior of the drawn sheets. From these results, it was estimated that the mechanical properties of biaxially laminated polypropylene sheets equaled the performance of aramid and carbon fiber composites, The roll-drawing process appears to be economically attractive for the production of ultra-high modulus crystalline thermoplastics in sheet form having excellent uniaxial or biaxial properties.
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    Polymer Engineering and Science 27 (1987), S. 684-691 
    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 thermotropic liquid crystalline polymer (LCP), when added to polystyrene (PS), can function as both a processing aid and a reinforcing filler. Thermal, rheological, and mechanical properties of the pure components and blends containing up to 10 percent LCP are reported. The LCP used is immiscible with PS, and when an extensional component of flow is present during processing, the LCP forms an elongated fibrous phase oriented in the flow direction. This oriented phase lubricates the melt, substantially lowering the viscosity. When the processed blend is cooled, the dispersed fibrous LCP phase is preserved in the solidified material. The LCP microfibers behave like short reinforcing fibers to improve the mechanical properties of the blend; for example, at an LCP concentration of 4.5 percent, the modulus is increased about 40 percent vs. pure PS.
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 27 (1987), S. 788-795 
    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: Curing reactions of epoxy resins are accelerated by added hydrogen-bond donor solvent and hydroxyl groups produced during the course of polymerization. A kinetic model comprising several different polycondensation and polyaddition reactions that occur simultaneously is developed. The concept of diffusion controlled reactions is employed to describe the change of reaction rate constants with conversion after the formation of an infinite crosslinking network. Good agreement is obtained between the model predictions and experimental data available in the literature.
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    Polymer Engineering and Science 27 (1987), S. 804-809 
    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 specific essential works of plane stress ductile tearing of several high- and ultrahigh-molecular-weight polyethylenes were obtained from deeply edge-notched tension specimens, with either single or double notches, by extrapolating the straight line relationship between the total specific fracture work and ligament length to zero ligament. Provided the fracture morphologies of the torn ligament are not widely different, the specific essential work (we) is a material property dependent on thickness but independent of specimen geometry. The specific essential fracture work also can be identified with Jc the critical value of the J-integral along a contour immediately bordering the fracture process zone at the crack tip. There is good agreement between the experimental we values and theoretical Jc estimates for these polyethylene materials.
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    Polymer Engineering and Science 27 (1987), S. 829-836 
    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: To przoduce efficiently high quality structural parts from fiber-reinforced epoxy materials systems, it is necessary to develop detailed process models. One key component in any such model involves the prediction of the cure kinetics, which in turn governs the viscosity, resin flow, void formation, and other important processing parameters. In this study, a series of isothermal and dynamic differential scanning calorimetry experiments was performed using Hercules 3501-6 and 3502 resins (TGDDM epoxy with DDS curing agent). The hypothesis of a dispersion of growing microgel particles, which become a continuous-phase solid at the gel point, was used as a basis to apply the Avrami theory of phase change to describe the polymerization kinetics up to the gel point. The extended equations for nonisothermal conditions properly accounted for the temperature effects on the kinetics. Comparison of the theoretical predictions with experimental data suggests that the Avrami theory of phase change may model adequately the cure kinetics of these systems, at least up to the gel point.
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Polymer Engineering and Science 27 (1987), S. 887-892 
    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 orientation development in elongational flow (spinning) of liquid crystal polymers (LCP) has been studied and a physical model derived which relates the modulus development and extensional deformation. The model defines an orientability parameter, λ, which in addition to the total elongational deformation (drawdown ratio) are related to the orientation (modulus) level of the final spun fiber. Five LCPs were included in the study - a lyotropic polymer: Poly (p-phenylene-terephthalamide) and four wholly aromatic naphthalene-containing polyesters. The experimental results have shown good agreement with the proposed model and indicate that λ is independent of the spinneret size and is characteristic of the orientability in elongational flow of each of the polymers investigated.
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    Polymer Engineering and Science 27 (1987), S. 913-916 
    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 drawing of an amorphous copolyester based on poly(ethylene terephthalate) and poly(1,4 cyclohexylene-dimethylene terephthalate) has been studied at temperatures from 20° to 100°C and various strain rates. The tensile properties, densities, and stress whitening of the stretched samples depend on whether the drawing temperature is below or above the glass transition temperature.
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    Polymer Engineering and Science 27 (1987), S. 925-933 
    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 functional group approach that accounts for the formation of higher oligomers was used in modeling the batch polymerization of melamine and formaldehyde. Five rate constants are required instead of 24 as needed in earlier studies to fit experimental data in the entire range. The model presented allows the formation of higher oligomers even though their formation is small. The batch polymerization of melamine and formaldehyde was studied under a wide variation of reaction parameters to find conditions that would lead to formation of higher oligomers preferentially.
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    Polymer Engineering and Science 27 (1987), S. 693-702 
    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: Heats of mixing of a variety of solvents with dimethyl methyl phosphonate, DMMP, are presented. A qualitative correlation between the exothermicity of the heat of mixing of DMMP with a particular solvent and sorption of DMMP by polymers containing structural units analogous to the solvent is observed. By this approach, polymers containing acidic hydroxyl functionality, such as phenol-formaldehyde condensation products and poly(styrene-co-vinyl benzyl hexafluorodimethyl carbinol), were identified as good sorbents for DMMP. Sorption isotherms, measured for these materials by the piezoelectric method, show enhanced sorption at low vapor activity and 135°C compared to polystyrene and poly(vinyl chloride) which lack these acidic sites and whose solvent analogs mix more endothermically with DMMP.
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    Polymer Engineering and Science 27 (1987), S. 727-730 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In a continuation of previous work (1), the melting and crystallization behavior of the layered oxidized skin on thermally oxidized inner wall surfaces of different high density polyethylene (HDPE) pipes was studied. By hot stage polarized light microscopy on 5 μm thick cross-sections of the skin, melting was shown to proceed successively as a front moving inwards as temperature was raised. Analogously, crystallization of the skin layers proceeded with the front advancing outwards towards the skin surface at decreasing temperature. The kinetics were followed and the data was compared with previous DSC thermograms (1) on similar samples. The high temperature melting peak of the oxidized skin reported in earlier DSC-work (1) is shown to be associated with material with normal spherulitic texture.
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    Polymer Engineering and Science 27 (1987), S. 764-771 
    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 number of studies on the kinetics of physicochemical processes are described. The methods used are shown to be potentially useful for making time-temperature predictions and for optimizing process variables. Examples described include (1) the long-term prediction of the performance of a plasticized polyvinyl chloride and doped polyacetylenes; (2) the polymerization of a monomer and the optimization of time, temperature, and initiator concentration variables; (3) analysis of an order/disorder transition in a thermochromic polymer; (4) the crystallization of polymers and the effect of a nucleating agent; and (5) the crystallization of an amorphous metallic glass. The theoretical background, significance, scope, and limitations of these measurements are also discussed.
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    Polymer Engineering and Science 27 (1987), S. 1050-1058 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An approach for modeling and simulation of multifilament melt spinning of poly(ethylene terephthalate) fibers is presented. It is shown that the quench conditions seen by the filaments within a bundle are not identical but differ for different rows of filaments. This, in turn, affects the spun fiber properties and introduces a degree of variability in the properties. The proposed approach allows determination of both the average properties and their variability for a given set of spinning conditions, spinneret geometry, and quench details.
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    Polymer Engineering and Science 27 (1987), S. 1088-1094 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of die wall temperature on the extrudate swell of polymer melts flowing through dies with single and dual circular channels was studied. Extrudate swell was measured at constant flow rates using an Instron capillary rheometer with a modified die section. It was found that under isothermal conditions, extrudate swell plotted against the average wall shear stress gave rise to a temperature independent correlation for polystyrene. Under non-isothermal conditions, such a correlation did not exist, which might be due to the change of wall shear stress in the axial direction. The extrudate swell in the non-isothermal cases can be better correlated with the wall shear stress at die exit. For the two-hole die, changes of die wall temperature varied both the flow rate ratio and the extru date swell ratio. The latter is, however, much less sensitive to the die wall temperature than the former.
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    Polymer Engineering and Science 27 (1987), S. 1113-1120 
    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 nonlinear finite element model for the static analysis of football helmets is developed as a first step in a methodology for the mathematical modeling of helmets. Polycarbonate and acrylonitrile-butadiene-styrene are considered as the shell material for the helmet. Such a methodology can be used to predict helmet response to loading and impact and can be incorporated in a computer program studying injuries caused by helmeted head collisions in football. Numerical results in terms of force-deflection curves, maximum stresses, and work of deformation are given. The influence of the polymeric material forming the helmet shell on energy absorption is studied. The effect of the internal padding material and suspension system is also considered.
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    Polymer Engineering and Science 27 (1987), S. 1141-1147 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The dependence of polymer-solute interactions on temperature In the range was 66 to 96°C was studied by inverse gas chromatography (IGC). A correlation equation was developed for estimation of the specific retention volume of nonpolar and slightly polar solutes in polybutadiene (PBD). Using equation of state solution theory, thermodynamic interaction was discussed in terms of contact energy and equation of state contributions in polybutadiene/solute systems. It was found that equation of state theory serves better than the Flory-Huggins theory as a comprehensive model to describe the temperature dependence of thermodynamic interaction.
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    Polymer Engineering and Science 27 (1987), S. 945-954 
    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: Isothermal differential thermal analysis (DTA) is well known for measuring thermal stability of polyolefins by determining the oxidative induction time at elevated temperatures. Oxidative induction time, measured up to 7,000 hours and over a temperature range from 240°C to 120°C, has been used to study the stability of polybutene-1 and crosslinked polyethylene in the melt state. The Arrhenius plots of DTA results show that straight line extrapolation from high to low temperatures is not possible. Thermoanalytically measured oxidation induction times and mechanical failure in oven aging experiments agree for polybutene and crosslinked polyethylene, Measurements of molecular weight and of mechanical properties of polybutene-1 during the induction period of oven aging experiments at low temperatures revealed that molecular weight and tensile properties are not sensitive indicators for the beginning of aging. The state of deterioration can be estimated easier by measurement of residual lifetime in the isothermal DTA experiment. Diffusion processes of stabilizers in polyolefins, as well as the consumption of stabilizer at elevated temperatures, especially during the induction period also was observed by DTA. Finally the extraction of stabilizer by hot water was measured by isothermal DTA.
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    Polymer Engineering and Science 27 (1987), S. 979-983 
    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: Soft, deformable padding materials are widely used for the fabrication of cushions and pads used to reduce contact loading stresses in several industrial and biomedical applications. This paper, presents an indentation technique that can be used to evaluate cushioning materials. The technique uses a soft-headed indenter made of poly(vinyl chloride) gel that is impressed upon the polymer cushion to be tested. The strain fields and the high stress regimes that develop in the head are then mapped using a grid technique and finite strain theory. Results of indentation tests carried out on a number of cushions of varying stiffness are presented and analyzed.
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    Polymer Engineering and Science 27 (1987), S. 1015-1017 
    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 elastic modulus of glassy polymers can be calculated from a measurable thermal property of polymers. The correlation of heat capacity jump data with molar modulus of 13 polymers indicated that the calculation of molar modulus from heat capacity jump energy for other glassy polymers is possible.
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    Polymer Engineering and Science 27 (1987), S. 1043-1049 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The rheological response of random copolymers of styrene and butyl methacrylate containing carbon black simulates the behavior of toner in the electrophotographic process. Both the relative viscosity and the dependence of viscosity on shear rate were increased by raising the temperature and raising the concentration and surface area of carbon black. For high concentrations and surface areas of carbon black and at elevated temperatures, a well-defined yield stress varied from 2.5 × 102 to 1.6 × 104 Pa, depending on the concentration and nature of the carbon black but independent of the type of polymer and temperature, implying the formation of a carbon black network. Plasticization by carbon black was favored at low surface area and concentration of carbon black and at elevated temperatures.
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    Polymer Engineering and Science 27 (1987), S. 1265-1274 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: We studied solvent-induced crystallization (SINC) in a compatible blend of poly (butylene terephthalate) (PBT) and a polyarylate (PAr) over a range of blend compositions and temperatures; liquid acetone was the crystallizing agent. Acetone transport kinetics were followed by mass uptake measurements in thin films and by optical microscopy. Crystallization kinetics were followed by density measurements. For the 0.2 mm thick films used, those with higher weight fractions of PST (50 to 60 percent by weight) exhibit diffusion controlled transport and crystallization over the entire range of temperatures studied (0 to 55°C). Those with lower weight fractions of PBT (∼30 percent by weight) display Case II sorption and crystal growth controlled crystallization at 0°C. The latter is rare for SINC in homopolymers and results from a sharp reduction in the PBT crystallization rate in the presence of the noncrystallizable PAr.
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    Polymer Engineering and Science 27 (1987), S. 1310-1316 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A model of a granular bed is used to obtain an estimate of the speed of propagation of intergranular stress waves. In the analysis, a simple elastic contact between neighboring grains is assumed. The model may be extended to include more complex Intergranular interaction mechanisms, but at the expense of such a simple analytical solution as that obtained here. The predicted dependence of compression of a granular bed on compressive load is compared with experimental measurements and is found to describe the relationship very well. The simplified analysis gives a general insight into the dependency of wave speed on bed geometry, indicating for example that while wave speed is independent of grain size, it does depend on the Initial porosity of the bed.
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    Polymer Engineering and Science 27 (1987), S. 1681-1687 
    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 failure modes and failure sequences for polycarbonate specimens loaded by a clearance-fit pin were investigated. Specimens were tested in various configurations to produce failures by different engineering failure modes. Photographs of the isochromatic fringe patterns were taken at different levels of damage development to examine the failure modes. A finite element stress analysis was used to explain the observed failure onset modes. Damage onset predictions were made based on a modified von Mises criterion. Failures involving net-tension damage initiated in the net-tension mode and failed ultimately in the same mode. Cleavage failures were observed for specimens with very small end-distances. Bearing failures were preceded by damage onset in a net-tension mode. Certain large-hole specimens failed in a buckling failure mode.
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    Polymer Engineering and Science 27 (1987), S. 155-164 
    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 scheme is presented for characterizing multiaxial nonlinear viscoelasticity of solid polymers in a manner suitable for application to the prediction of deformation of polymeric parts. The basis of the scheme is the systematic exploitation of simplifications resulting from: (1) restrictions on the class of stress histories considered, (2) material symmetry (e.g., isotropy), and (3) the nature of viscoelastic nonlinearity in any given material. Several classes of stress history are considered. In the special case of inplane response of an isotropic material to a two-dimensional proportional loading history, it is shown that the nonlinearity can be expressed through the dependences of compressibility B and shear compliance J on two invariants of the stress history: I1 and I2′, which separately characterize the magnitudes of hydrostatic and deviatoric components of the stress tensor. When this approach is applied to the description of biaxial creep and recovery of isotropic polypropylene, it is found that for strains up to 0.012, B is independent of I1 and I2′, while J is linearly related to I1 and I2′. These results are used to predict axial strain and hoop strain in the wall of a pressurized pipe, and the predictions compared with those obtained with three approximate procedures.
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  • 77
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    Polymer Engineering and Science 27 (1987), S. 271-276 
    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: Fatigue testing of polymers has revealed significant differences between the fatigue response of polymers and metals. Generally, fatigue failure in metals is a process of crack initiation, propagation, and failure. Also, fatigue damage in metals is cumulative and cycle dependent, but remains essentially independent of test frequency. Unlike that of metals, the fatigue behavior of polymers is influenced by viscoelastic effects. At high frequencies, softening and melting occur, and fatigue failure depends largely on the test frequency. At lower frequencies, fatigue failure becomes less sensitive to test frequency and results from crack initiation and propagation. These polymer characteristics arise from the production of hysteresis energy during fatigue. A portion of this energy is released as heat, some of which is dissipated, but most is absorbed in the sample, raising its temperature. This temperature rise leads to degradation of the material and a short fatigue life. Experiments were conducted to measure hysteresis energy and temperature rise for a talc-filled polypropylene. A mathematical model was developed to calculate the energy and temperature distribution during fatigue. Correlation of the temperature rise predicted by the model with that observed experimentally provided values for the various energy terms that quantitatively defined the thermomechanical fatigue response of this polymer.
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  • 78
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    Polymer Engineering and Science 27 (1987) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 79
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polymer devolatilizers are in widespread use in the polymer industry for removing solvents and monomers from polymer melts prior to product fabrication. Design equations for describing the solvent flux usually include both the diffusion coefficient of the solvent in the polymer melt and the equilibrium concentration of the solvent at the polymer-vapor interface. Several models make the as sumption that the solvent diffusivity is constant over the ranges of solvent concentrations and temperatures in the devolatilizer. This is a critical assumption that may be difficult to check without obtaining diffusivity data at the operating temperatures and concentrations of the process equipment. There are three models that can be used for diffusion coefficients in devolatilizer design: the free volume model developed by Duda, Vrentas, and coworkers; a new linear model proposed in this study; and a constant diffusivity model, The linear model is obtained by combining a new correlation for solvent activity coefficients in molten polymers with free volume theory and linearizing the resulting equation. The error between using the complete free volume theory and using the linear model, or alternatively, using a constant diffusion coefficient, is calculated for several solvent-polymer systems. The linear model is convenient to use for determining the effects of the solvent activity coefficient on the diffusion coefficient. A method is presented for determining whether the complete model, the linear model, or the constant diffusivity model is appropriate for a given devolatilizer design.
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  • 80
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    Polymer Engineering and Science 27 (1987), S. 328-334 
    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: Information on the interfacial region in incompatible polymer mixtures can be gathered using various techniques including electron microscopy, thermal transition analysis, and more sophisticated methods such as nonradiative energy transfer (NRET). Selected examples are reported here to illustrate the exciting potentialities offered by diblock copolymer emulsifiers in controlling interfacial adhesion and devising high performance polymer blends.
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  • 81
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    Polymer Engineering and Science 27 (1987), S. 359-366 
    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: Ten commercial linear low-density polyethylenes (LLDPE) were characterized by solution viscosity, size exclusion chromatography, SEC, and 13C nuclear magnetic resonance. The resins were copolymers of ethylene with butene, hexene, or octene. They were prepared in gas phase (with narrow or very broad molecular weight distribution), or in solution. The macromolecules were found to be linear. For all but the very broad molecular weight distribution resins the average comonomer sequence length was found to be 1; in the other case diad formation was observed. The weight average molecular weights calculated from SEC, and intrinsic viscosities agreed quite well. Mechanical degradation of LLDPE was observed during the solution viscosity measurements.
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  • 82
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    Polymer Engineering and Science 27 (1987), S. 351-358 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An advanced hypothesis derived in Part I (this issue) is tested with selected model blends. Blends of copolymers of styrene and acrylonitrile (SAN) and poly(methylmethacrylate), (PMMA) were studied because they are both amorphous, thermally stable, have large density differences, are easy to cut (in an ultramicrotome) and because comprehensive studies have been reported In the literature on this system. The melt viscosity of the blends were studied using a Rheometrics Mechanical Spectrometer and an Instron capillary rheometer. Light scattering measurements were performed during flow in order to measure the critical transition stress. The phase structure of quenched samples was studied by transmission electron microscopy on ultramicrotome cuts. It was shown that an Interpenetrating co-continuous structure develops when flow is stopped, if a homogeneous phase Is formed during flow. Melt fracture limits the applicability of this approach to nearly compatible blends.
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  • 83
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    Polymer Engineering and Science 27 (1987), S. 389-390 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 84
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    Polymer Engineering and Science 27 (1987), S. 402-409 
    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 melt rheological behavior of chloro-polyether and polyepichlorohydrin blends was studied. It was found that both the coupled and uncoupled blends at different blending ratios are pseudoplastic, but there was a great difference in pseudoplastic behavior between them. All the blends obeyed the principles of temperature superposition and composition superposition for plots of shear stress vs. shear rate. A model is proposed to describe and predict the rheological behavior of the blends.
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  • 85
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    Polymer Engineering and Science 27 (1987), S. 391-397 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: By means of a twin-roll masticator and Brabender rheometer, the effect of chlorinated polyethylene (CPE) and polyethylene (PE) on the impact strength and processability of poly(vinyl chloride) (PVC) was studied. The experimental results show that CPE can promote the plasticity of PVC and the effect increases with the amount of CPE. Addition of a small amount of PE in PVC/CPE (100/12) makes an impressive improvement in the impact strength of the mixture. The impact strength of PVC/CPE/PE (100/ 12/2.5) at 20°C is 30.0 kJ/m2 higher than that of PVC/CPE (100/12). The dynamic viscoelastic spectra, tensile strength, and elongation test reveal that CPE is incompatible with PVC but may act as a compatibilizer for PVC/PE. The disperse state of the polyblend was studied by differential scanning calorimetry (DSC); it was found that the mixing sequence has an influence on the impact strength of the blend.
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  • 86
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    Polymer Engineering and Science 27 (1987), S. 398-401 
    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 compatibility, morphology, fusion behavior, and mechanical properties of blends of poly(vinyl chloride) (PVC), acrylic resin (ACR), and chlorinated polyethylene (CPE) (100/0-30/0-20) were studied. The experimental results show that the compatibility of the polyblend increases with the amount of ACR added. The blends composed of PVC/ACR/CPE (100/3-25/10-15) are fairly compatible. So far as impact strength is concerned, partially compatible blends are preferred.
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  • 87
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    Polymer Engineering and Science 27 (1987), S. 458-462 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An unusual compatibility was observed with the melt blends of propylene/α-olefin copolymer with isotactic homopolypropylene. The simple binary blend exhibits a single glass-transition temperature, and, by differential scanning colorimetry, a single melting and crystallization temperature over the entire blending ratios examined. Depending on the compositions, the characteristic temperatures vary between those exhibited by the component polymers. Vigorous annealings failed to phase separate the components. The melting behavior of the annealed polymer sample suggests the crystalline components of the two polymers are cocrystallized in this unique compatible system.
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  • 88
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    Polymer Engineering and Science 27 (1987), S. 485-492 
    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: Microcellular foam is a polymeric foam with bubble sizes of 10 microns or less that is produced by saturating a polymer with gas and then utilizing the thermodynamic instabilities that result when the polymer is heated and the pressure is reduced to nucleate the cells. A model for the nucleation of microcellular foam in amorphous polymers with additives has been developed. The nucleation process depends on the solubility, concentration, and interfacial energy of any additives present. At very low levels, additives in solution act to increase the free volume of the polymer, resulting in homogeneous nucleation within the free volume Well above the solubility limit, heterogeneous nucleation dominates, as it lowers the activation energy for nucleation to levels below that for homogeneous nucleation. In the vicinity of the solubility limit of the additive, these two nucleation mechanisms compete. The polystyrene-zinc stearate system has been chosen for experimental evaluation.
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  • 89
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    Polymer Engineering and Science 27 (1987), S. 504-509 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The prediction and measurement off the developing radial temperature profile in a single-screw extruder is essential since excessive extrudate temperature and poor temperature uniformity at the die affect the quality of coextrusion and film/sheet extrusion processes. A finite-difference scheme is used to predict the development of the radial temperature profile in the metering section of a single-screw extruder for power-law fluids. A finite-element analysis of the flow around the screw-tip transposes this temperature profile onto an on-line temperature measuring device consisting of 10 thermocouples for a comparison of numerical results with experimental data on polycarbonates.
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  • 90
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    Polymer Engineering and Science 27 (1987), S. 524-528 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some engineering thermoplastics cannot be easily processed by injection molding because of their high viscosity. This is the case for Ultra-High Molecular Weight Polyethylene (UHMWPE). Parts are either compression molded or machined from extruded shapes. Over the years, forging has been increasingly used to produce more or less complicated parts. Forging is a process in which a preform is subjected to bulk deformation in constraining dies, by applying heat and pressure, but with the polymer remaining in the solid (semi-crystalline) phase. To fabricate acceptable mechanical components such as gears and sprockets, a close control of the operating conditions and a good prediction of shrinkage are necessary, For a better understanding, a study has been conducted on forged UHMWPE disks and gears. Parameters such as material and mold temperatures, dwell time, speed of forging and dwell pressure were investigated. Results show that material and mold temperatures are the most important parameters. For gears, optimization of processing conditions led to a shrinkage of ∼0.2 percent, measured on pitch diameter. The effect of post-annealing at various temperatures is also reported.
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  • 91
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    Polymer Engineering and Science 27 (1987), S. 586-597 
    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 parallel-plate constant-stress rheometer is used to measure the yield stress τy, and the post-yield flow curve T(\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}), where τ is shear stress and \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} is shear rate, for microphase-separated triblock copolymer melts. Five polymer samples, all styrene-butadiene-styrene but with differing composition ratios and molecular weights, are tested at 125°C. Specimens are prepared by casting sheets from solutions made with different solvents. The τ(\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}) is found usually to be sigmoidal, for the range 10-5 〈 \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} 〈 10-3 s-1, representing different stages of microstructural degradation in flow. Measurements indicate that a true τy exists, with values in the range 100 〈 τy 〈 500 Pa for these melts. A general trend is detected for τy to decrease as the casting solvent solubility parameter increases. A scheme for correlating the dependence of τy, on composition and molecular weight is proposed for the various polymers. For selected samples, the effect of mechanical history (sequence of stress application) and a temperature variation that crosses Ts (110 to 150°C) are also explored.
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    Polymer Engineering and Science 27 (1987), S. 617-617 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 93
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    Polymer Engineering and Science 27 (1987), S. 627-631 
    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 series of blends was prepared with broad concentration ranges of polycarbonate (PC) and styrene-acrylonitrile copolymers (SAN) containing 5.5 and 30 weight percent acrylonitrile (AN). These blends were then injection molded, and their properties were measured and correlated with the morphologies of the blends (as determined by transmission electron microscopy). The toughness properties were shown to be discontinuous and very sensitive to composition of the continuous phase in the blends. The dart impact toughness remained high up to 30-40 weight percent SAN and dropped rapidly above this SAN concentration. The notched Izod toughness fell off rapidly at 10 weight percent SAN and greater. The strength and modulus had a more linear dependence on composition. Results of studies of the Tg by differential scanning calorimetry (DSC) show the presence of two phases over the entire concentration and a small solubility of each phase in the other. The heat distortion temperature under load (DTUL) of the blends approximated a linear additivity curve for the components. As expected, the blends had much better clarity where the refractive indexes more nearly match (in the case of the 5.5 percent AN copolymer).
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    Polymer Engineering and Science 27 (1987), S. 647-652 
    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 formation, mechanical properties, thermal characteristics, and density of diffuse shear banded zones of polystyrene, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and their miscible blends were studied. A significant increase in density of 0.2 to 0.3 percent was found for the diffuse shear banded zones. Differential scanning calorimetry results revealed a volume recovery process that occurs below Tg for the diffuse shear banded zones. The post-yield-stress drop, anelastic shear strain within the zone, and anelastic tensile strain were all found to decrease with increasing PPO content in an identical manner. The sharp shear band to diffuse shear banded zone transition was related to chain mobility, molecular packing, and free energy as manifested in the post-yield-stress drop. The decrease in anelastic shear strain with increasing PPO content for the blends is possibly related to the beta transition and length between entanglements.
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  • 95
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    Polymer Engineering and Science 27 (1987), S. 663-668 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polymer-polymer blends offer a route for enhancement of various properties. When immiscible polymers are blended together (in the presence of a compatibilizer), the blend properties are dependent on the morphology of the phases. Uniform, fine dispersions generally result in “average” properties. Discussed here are blends of polyamides or polyesters with polyolefins, particularly polyethylene, where small amounts (3-20 percent) of the former polymers dispersed as essentially parallel, thin, large laminae produce substantial reduction (3-100 times) of permeability properties in blow-molded/extruded articles. Physical properties of such blends, their permeability properties, and morphologies are discussed.
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    Polymer Engineering and Science 27 (1987), S. 673-683 
    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 diisocyanate, 1,4-eyclohexane diisocyanate (CHDI), has been used in a series of polyether-based polyurethane elastomers. The slightly opaque samples are semicrystalline in nature with high performance properties, including high softening temperature, very good thermal stability, high tensile and tear strengths, excellent solvent resistance, and low hysteresis in compressive fatigue. Polymer properties are in part due to the small, compact, symmetrical structure of the aliphatic CHDI. Comparison of the physical, mechanical, and thermal properties of polyurethanes prepared from the aliphatic diisocyanate 4,4′-dicyclohexylmethane dilsocyanate (H12MDI) reveal the H12MDI polymers to be more flexible and transparent elastomers with lower softening temperatures and tensile moduli and higher hysteretic heat build up. They are generally soluble in organic solvents.
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  • 97
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    Polymer Engineering and Science 27 (1987), S. 716-726 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Experimental results on reactions forming polyurethanes and polyurethane-polyester Interpenetrating polymer network (IPN) are discussed with particular interest in rheological and kinetic changes before the gel point. In the IPN formation, viscosity rise is affected by the amount of styrene and polyester in the reaction system. Plots of reduced viscosity vs. conversion do not fall into a single curve. The results may be explained by the concept of having intra-molecular reaction or ring formation. The existence of hydroxyl group at the end of polyester molecule causes the graft reaction between the polyurethane phase and the polyester phase, which may speed up the viscosity rise of the reactive system. A simple method which based on rheological measurements only is proposed. This method of plotting reduced viscosity vs. reduced reaction time provides similar results as in the plots of reduced viscosity vs. conversion.
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    Polymer Engineering and Science 27 (1987), S. 731-739 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental procedure is suggested for quantitative evaluation of the interdependence of stresses and moisture diffusion in polymer-dominated materials with special emphasis on epoxy resin based polymeric adhesives. It has been found that when such material is stressed in tension, the moisture diffusion rate increases; and when in compression, it decreases. At low stress levels, a linear relation was obtained between the coefficient of moisture diffusion and the applied stress, while at elevated levels it is nonlinear. Throughout the loading range, the coefficient correlates well with the volumetric changes in the stressed material.
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  • 99
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    Polymer Engineering and Science 27 (1987), S. 740-752 
    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 polycondensation stage of polyethylene terephthalate (PET) formation is assumed to include side reactions leading to the formation of diethylene glycol, vinyl end groups, and acid end groups, in addition to the usual polymerization of bis (2-hydroxyethyl) terephthalate (BHET) in semi-batch reactors. A, flexible objective function has been proposed with temperature and pressure as control variables. Computations from the first variation technique show that the pressure should be reduced to the lowest limit under all possible conditions. Consequently, optimal temperature profiles in batch reactors are obtained for various lower limits of reactor pressures using the combination of first and second variation techniques. For the first variation technique, the vector iteration method of computation was used, and the near optimal profile so obtained was used as the initial guess for the second variation technique. The result of optimization shows that the lower limit of pressure and weighting parameters appearing in the objective function have profound effects on the optimum profiles. For higher pressures, it is shown that a high temperature must be used initially; but must be lowered later to minimize the formation of side products. However, for lower pressures, the temperature must be increased from a low value initially; but for large polymerization times, the temperature must be further reduced to minimize the formation of side products. It is thus seen that the optimum temperature profile for low pressures exhibits a broad maximum.
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    Polymer Engineering and Science 27 (1987), S. 848-856 
    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 mechanical behavior of bisphenol-A-polycarbonate has been studied. The principle mode of deformation studied was fatigue with monotonic tests and stress relaxation tests also performed. Testing was conducted at different strain rates and polycarbonate was found to be a rate sensitive material. In addition, it was found that polycarbonate's data show a good fit to the rate process theory of deformation first proposed by Eyring, whereby molecules move over a potential barrier in an activated process. A hard ball model is presented as a first approximation to this activated process of deformation. Finally, a potential mechanism of deformation during fatigue loading is discussed.
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