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  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 989-999 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reaction kinetics of radical chain copolymerization of t-butoxycarbonyl-oxystyrene (TBS) and sulfur dioxide have been studied using a reaction/sampling apparatus that permits accurate determination of the reaction mixture concentrations during polymerization. The results are compared with the styrene-sulfur dioxide copolymerization kinetics. The influence of temperature and reactant concentrations on the polymerization rate and copolymer composition are reported. With increasing reaction temperature, the amount of SO2 incorporated and the molecular weight fo the copolymer are found to decrease. For a constant TBS concentration in the reaction solutio, raising the SO2 concentration causes an increase of SO2 incorporation in the copolymer, up to a maximum SO2 content corresponding to a TBS:SO2 mole ratio of 2:1. However, for a constant SO2 concentration, the amount of TBS incorporated in the copolymer increases with decreasing TBS concentration in the reaction solution. The polymerization rate and copolymer molecular weight increase proportionally with monomer concentration as expected for a normal radical chain polymerization mechanism. Comparison of these findings with various kinetic models for styrene-SO2 copolymerization indicates good agreement with models proposed by Barb (1-3) and Walling (4); however, the data do not agree with the predictions of Matsuda et al. (5) The understanding of the kinetics and reaction mechanism provided in this study will aid in the manufacture of this lithographically important copolymer.
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1000-1004 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Neutron reflectivity (NR) was applied to measure te concentration of water at the buried interfaces between an amorphous poltimide and silicon single crystal wafers. Excess water was discovered within 30 Å of the metal/polymer interface, where the water concentration reached 17% (by volume) for the samples without a coupling agent and 12% for the ones with coupling agent. Beyond the interface, the water concentration was measured at2 to 3%, which is typical of bulk polyimide. The above results demonstrate conclusively the unique power of NR in determining water concentration near a buried interface, and provide the first quantitative evidence for a water concentration profile which peaks in the interface region.
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  • 3
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1005-1010 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 photocrosslinking precess for polyethylene and its industrial irradiation apparatus has recently been developed and used successfully in the manufactre of thin wall crosslinked polyethylene-insulated wires. Polyethylene (PE) resin with the desired amounts of additives, such as photoinitiator, multifunctional crosslinker, and antioxidant is mixe homogeneously. The amixture of PE is granulated, and then extruded on a conductor wire. The coated PE layer in the melt is subsequently irradiated in a specially designed UV irradiation apparatus for 5 to 10 s. The studies show that the photocrosslinked PE-insulation high voltage television wires produced by this new technique possess excellent electrical and mchanical properties and much lower operating cost compared with wires produced by the electron beam crosslinking technique.
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  • 4
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1011-1015 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this paper we investigate a new approach for the automated sorting of post-consumer plastic waste. We show that rapid and relible identification of polymers can eb achieved using a combination of fixed-filter near-infrared spectroscopy and neural network data analysis, and we demonstrate the effectiveness of the proposed method for sorting polyethylene terephthalate, high density polyethylene, and poly(vinyl chloride). Finally, we discuss a proposed compact, rugged instrument based on the new sorting method. Owing to the flexibility gained by incorporating neural networds in our system, thismethod can easily be extended to include additional polymers.
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  • 5
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 506-512 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential scanning calorimetry (DSC) analysis has been performed on modified and commericial amorphous samples of poly(ethylene terephthalate) (PET) crystallized by high pressure carbon dioxide (CO2). Two endothermic peaks are present in the DSC scans of all the carbon dioxide-treated samples. A qualitatively analogous behavior has been detected in the case of amorphous samples heat treated at temperatures slightly exceeding the glass transition temperature of virgin material. Wide angle X-ray scattering analysis has confirmed the structural analogies between samples CO2 crystallized at 50°C and thermally crystallized slightly above Tg. A differential scanning calorimeter capable of working at high pressure of CO2 has been adopted in order to examine the effect of carbon dioxide on the crystallization temperature range.
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  • 6
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 linear viscoelastic behavior of commercial broad-distribution polypropylenes is studied. The samples underwent different controlled peroxide degradation rates, so they exhibit different molecular distributions. The relaxation spectrum is obtained by assuming that it takes the shape of a Log-Normal distribution. It is in agreement with the linear viscoelasticity theory by providing limiting values, contrary to other models. Moreover, the ratio τw/τn which takes place in this law is very useful to distinguish the synthesis differences of the samples when the Melt Flow Index alone cannot.
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  • 7
    Electronic Resource
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1022-1030 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 dynamic simulation method has been developed of the fracture process of a fiber in a flow field using the particle simulation method proposed i a previous paper. The fiber is modeled with bonded spheres as a fiber model. The flexibility of the fiber model is altered by changing three parameters of the stretching, bending, and twisting constants between adjacent spheres. The stress induced in each bond of the fiber model as a result of deformation is formulated using displacement of the bodn distanc, bond angle, and torsion angle fr each pair of spheres. After deformation, the fiber model fractures at the bond at which the stress surpasses the strength of the fiber. The motion of the fiber model in a flow field is determined by solving the translational and rotational motion equations for individual spheres under the hydrodynamic force and torque exerted on them. The correctness of the method and formulation was verified by comparing the simulated deflection curve of a cantilever beam (with a concentrated load at the end) with the theoretical curve. Good agreement was found in both the deflection and slope of the beam. The fracture process of a fiber after bending deformation in a two-dimensional siimple shear flow was simulated under assumptions of an infinitely dilute system, no hydrodynamic interaction, and a low Reynolds number of a particle. The calculated critical conditions of the flow field for fiber fracture were compared with Forgacs and Mason's theoretical ones. Simulated values of the fracture condition of the fluid shear stress related to the Young's modulus of a fiber agree with theoretical ones over an aspect ratio of 15.
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  • 8
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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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  • 9
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 546-554 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 creep characteristics of polycarbonate at elevated temperatures are investigated. The onset of glass transition temperature of polycarbonate is determined. An Arrhenius type relationship is used to describe the creep process and the concept of property retention index as applied to creep is discussed. An attempt is made to construct the master rupture curves for polycarbonate. The onset of glass transition temperature of polycarbonate was placed at around 110°C. It is concluded that the Arrhenius theory and the concept of property retention index are extremely useful in the construction of master rupture curves and that they require further investigation.
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  • 10
    Electronic Resource
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1061-1065 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 choice of photoinitiators is partly governed by the requirement of a high curing speed. Many reactive monomers and efficient photoinitiators have been synthesized and are commercially available. However, improved photoinitiator systems, exhibiting increasingly faster curing speeds and/or increased photosensitivity, are increasingly required. The intrinsic reactivity in the exicited states determines te interest of a given photoinitiator with reference to its efficiency. However, other factors e.g. high molecular absorption coefficients and a broad spectral absorption range, synergistic effects, yellowing, extractability, and th effect on the long-term stability, must be considered as important. An attractive field of research and development is found in the role played by decisive parameters affecting the reactivity of a given structure, such as chemical substitution in well-chosen positions, the character of water solubility, acid release ability, and copolymerization potential. Laser spectroscopy proved a most convenient tool for the real time investigation of the excited state dynamics and the processes involved.
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  • 11
    Electronic Resource
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1053-1060 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Since poly(tetrafluoroethylene) (PTEE) and its copolymers are soluble only at high temperatures in primarily perfluorocarbon solvents, direct measurement of their molecular weight distribution by conventional dilute solution techniques is not possible. Instead, the structure must be inferred from the linear viscoelastic properties of the melt. To make this inference, the spectrum must be determined over a wide enough range of relaxation times t include the plateau modulus, GNO. This is accomplished by time-temperature superposition for most polymers. For PTFE and its copolymers, the range between the melting point and th degradation temperature is too narrow for time-temperature superposition to be used reliably for determination of the high frequency response. Hence, as they do not exist in the melt state over a wide enough temperature range for superposition, their viscoelastic properties at high frequencies must be measured directly. A new technique employing a piezoelectric ultrasonic composite oscillator has been developed. The viscoelastic Properties, G′(ω) and G″(ω), of Tefzel 280 (a high molecular weight ethylene-tetrafluoroethylene copolymer) have been measured at ultrasonic frequencies (40 to 200 kHz).
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  • 12
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 144-150 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 objective of the current paper was to extend the relationships between complex polymer structures and microwave absorptivity that were formulated in the first three papers of this series (1-3). The microwave processing of composite and polymeric blends via a cylindrical resonance wave cavity and a rectangular standing wave applicator is described. These polymeric materials were irradiated in a low power (〈 100W) electric field at 2.45 GHz. Graphite-epoxy laminates were processed in both standing and traveling wave applicators. Rapid heating and curing were achieved in both cases. An observation of significance was that, with proper tuning of the traveling wave device (the precursor of a protable repair tool), it proved to be highly effective in processing. Additionally, a compatible blend of poly(methyl methacrylate) and poly(vinylidene fluoride) was heated in and applicator and the rates of temperature rise were demonstrated to depend upon morphology.
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  • 13
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1077-1085 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Double yield points before necking were observed in injection molded specimens of poly(tetramethylene terephthalate) (PTMT) and its copolymers under tensile loading. The first yield is associated with deformation of the amorphous region and the second yield is caused by the alpha to beta transition of PTMT crystallites. The first yield point became less apparent with an increase of crystallinity of the specimens. The second yield point became more apparent with an increase of crystallinity. Annealing of injection molded specimens increased the crystallinity and increased the second yield point on stress-strain curves. Copolymerization decreased the crystallinity and made the first yield point more prominent. Effects of annealing on mechanical and thermal properties of the specimens were also measured. The specimens changed their properties from ductile to brittle during annealing. Their change during annealing was mainly attributed to the increase of crystallinity and not to thermal degradation and/or crosslinking.
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  • 14
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 587-597 
    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: The copolymerization of n-butylmethacrylate with 2-hydroxypropylmethacrylate was studied in a closely intermeshing counterrotating twin-screw extruder. The average molecular weight of the product can be increased by increasing the screw rotation rate or the die resistance or by decreasing the throughput or the barrel temperature. The conversion can be improved by decreasing the throughput, increasing the die resistance, and (within limits) increasing the barrel temperature, as well as through post-initiation. Compared with various classical polymerization processes, this situation requires that particular attention be paid to the occurrence of a gel effect, the existence of a thermodynamic ceiling temperature, and the reactivity ratio of the monomers used.
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  • 15
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1086-1097 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 comprehensive study of toughening unsaturated polyster and vinyl ester resins by addition of liquid rubbers was carried out by considering the effects of cure temperature and gel time on final resin/rubber morphology. The objective was to produce a dispersed rubber phase consisting of particles less than 15 μm in diameter with the addition of limited amounts of rubber, so as not to seriously reduce the modulus and strength of the base resin. A variety of liquid rubbers was used including those based on poly(butadiene acrylonitrile), poly(epichlorohydrin), and two poly(acrylates). Fracture toughness of unmodified and rubber modified materials was measured using the compact tension (CT) test geometry. Significant improvements in fracture toughness were achieved with little to no change in Young's modulus or glass transition temperature. With modest rubber additions, the fracture toughness increased up to 62% for the polyester resin and up to 116% for the vinyl ester resin. In general, fracture toughness increases with increases in volume fraction of rubbery second-phase particles. However, results suggest that two-phase particles may be more effective tougheners than single-phase particles. The toughening mechanism appears to depend on the type of rubbery particle morphology present.
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  • 16
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1106-1112 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The present paper explores an effective means of characterizing structural changes of poly(vinyl chloride) (PVC) particles during gelation and fusion of PVC plastisols with small angle light scattering (SALS). The SALS method was shown to provide an in situ observation of swelling of PVC particles as well as quantitative information of average size of swollen particles while they are in progress of gelation and fusion. In addition, the SALS method enabled one to evaluate the relative solvent power of plasticizers from the manner of increase in the correlation distances.
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  • 17
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1113-1116 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 miscibility window of the 50/50 w/w poly(styrene-co-4-vinylphenyl)-dimethylsilanol/poly(n-butyl methacrylate) (ST-VPDMS/PBMA) blends prepared from toluene was studied and determined to be in the VPDMS composition range of 4 to 18 mole% in the copolymers. The observed miscibility window was to be compared to the range of 9 to 34 mole% found for the blends prepared from methyl ethyl ketone which was capable of competing for hydrogen bonding. The fact that the observed miscibility windows are influenced by the choice of solvents illustrates that an equilibrium state of polymer mixing is not always attained in solvent casting films and that caution needs to be exercised in studying polymer miscibility when solvent cast films are used.
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  • 18
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1117-1123 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Double yields, as well as other complex yielding behavior, that are observed during the tensile deformation of the polyethylenes have been studied in a systematic manner. The conditions under which such yielding is observed were established by studying a set of linear polyethylenes and well-characterized ethylene copolymers of narrow molecular weight and composition distributions. A wide range in crystallinity levels were developed and the rate of deformation and the deformation temperature were varied. These experimental results make clear why such complex yielding processes are not always observed. A qualitative explanation, based on the postulate of a partial melting-recrystallization process during deformation, is given that encompasses all of the experimental data.
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  • 19
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1124-1132 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 fracture behavior of polypropylene reinforced with 30% by weight of short glass fibers was studied using single and double feed plaque moldings. Plaques were injection molded using several gate types and gate positions. Fracture toughness Kc, was calculated at different positions in the plaque moldings using single edge notched tension specimens. Fracture toughness was assessed in the directions parallel and perpendicular to the mold fill direction through measurements of the load to produce complete fracture. Results indicated that the value of fracture toughness is affected by the type of gate as well by size of gate. Position of the specimen also affected fracture toughness. Generally, specimens taken from positions near cavity walls gave higher toughness values than those taken from the center of the moldings. Furthermore, fracture toughness in the transverse direction was consistently higher than in the melt flow direction. Finally, in the case o double feed moldings, a much higher fracture toughness was obtained when the initial crack was perpendicular to the weld line than when it was placed inside the weld line.
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  • 20
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 658-665 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Phase behavior, thermal, rheological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers from optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing 〈 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.
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  • 21
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 666-672 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 peel force of a PVDF/3-APS/Si joint and a PVDF/3-APS/Al joint can reach the same level by treating the Si substrate with ≥ 0.3% 3-aminopropyltriethoxy silane (3-APS) solution and treating the aluminum substrate with NH3 solution (pH 10.5) first and then with ≥ 3% 3-APS solution. Scanning electron micrographs show that the interfacial adhesion mechanisms of PVDF/3-APS/Si joints and PVDF/3-APS/Al joints are different. In the peel test, the PVDF [poly(vinylidene fluoride)] break surfaces from PVDF/3-APS/Si joints reveal striations on the surface and less plastic deformation. The significant plastic deformation of the PVDF at the break surface may result from the deeper interpenetration of 3-APS with PVDF in the PVDF/3-APS/Al joint than in the PVDF/3-APS/Si joint. The peel force of PVDF film/substrate joint depends on many factors: film thickness, peel rate, concentration of coupling agent, the treatment time of the coupling agent on the substrate, and the substrate pretreatment.
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  • 22
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 of the effect of crystallinity on the light scattering of regenerated cellulose tubular films is reported. Several films were prepared by varying manufacturing conditions, so that thickness and surface roughness were maintained approximately constant and the degrees of crystallinity varied between 38 and 66%. The scattered radiation intensity, measured between 220 and 550 nm decreases with the increasing wavelength. It was demonstrated that for the polymeric films studied, there was excellent agreement between crystallinity and scattering radiation intensity for a given wavelength. It was found that for crystallinity values less than around 57%, scattered radiation intensity decreases with increasing crystallinity, the reverse of that for crystallinity values greater than that percentage.
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  • 23
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1161-1166 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 temperature over the range -196 to 150°C on the crosslinking of polyethylenes irradiated by electron beam has been investigated on the basis of gel content determination and Fourier transform infra-red (FTIR) spectroscopy. The crosslinking efficiency increases significantly with increasing irradiation does and at elevated irradiation temperature. The crosslinking rates of high density polyethylene (HDPE) and low density polyethylene (LDPE) samples above the melting point (TM) are much higher than those below Tm. The FTIR data give positive evidence: (i) that trans-vinylene double bonds in cross linked HDPE and LDPE samples increase with increasing irradiation dose temperature (ii) that vinyl double bonds in HDPE decrease rapidly with increasing irradiation dose and temperature, and (iii) vinylidene groups in LDPE decrease slowly with increasing temperature at the lower dose and are almost independent of the irradiation temperature at above room temperature and the higher dose of more than 100 kGy. Gas bubbles are observed in LDPE samples irradiated at 100 and 150°C with high dose (200 to 250 kGy). The size of the bubbles increases gradually at high temperatures.
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  • 24
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 768-777 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 versatile transient network theory has been used as a framework for the interpretation of large amplitude oscillatory behavior of polyolefin melts in terms of their entanglement kinetics. The model reasonably describes all previously published measurements of the large amplitude oscillatory shear behavior on melts. Seven polyolefins are examined, three new materials and four previously studied. A qualitative difference in the nonlinear behavior in large amplitude oscillatory shear has been identified between the polyethylenes examined and the two other polyolefins, polystyrene and polyisobutylene.
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  • 25
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 703-708 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 reactor with surface renewal, originally designed for poly(ethylene terephthalate) (PET) polymerization, was applied for poly(butylene terephthalate) (PBT) polymerization. A comprehensive model including side reactions was developed and compared with the experimental results. The diffusivity of butanediol (BD) in PBT melt was measured separately by desorption experiments (Db - 1.08 × 106 exp(-32600 / RT) (m2/min)). Optimum operating temperature for PBT polymerization was found to be around 250°C in order to avoid degradation.
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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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  • 27
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    Polymer Engineering and Science 35 (1995), S. 709-721 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 rigorous solution of the diffusion of penetrant into a laminar film comprised of multilayers of m components is presented by an orthogonal-expansion method. As the simplest practical cases of m - 2 and m - 3, with stepwise distribution of both diffusion coefficients and solubility coefficients at the boundary between respective layers, the diffusion properties in the transient state are analyzed in detail. That is, changes in the penetrant concentration distribution within the laminar film and the total amount of penetrant sorbed within the film both with time after exposing the film to an atmosphere of fixed penetrant concentration are calculated for A-B as well as A-B-A type layer arrangements. The calculation is performed while keeping (L2/L1) at a constant value of 2.0 but varying the diffusion coefficient ratio of (D1/D2) from 102 to 10-2, and/or varying the solubility coefficient ratio of (S1/S2) from 1 to 10, where L1 and (L2 - L1) are the thickness D1 and D2 are the diffusion coefficients of penetrant, and S1 and S2 are the solubility coefficients in the A-component and B-component, respectively. The sorption curves deviate considerably from those of Fickian curves of homogeneous film with (D1/D2) - 1 in their respective ways. The results obtained here can be applied to the diffusion in a single component polymer film having a surface layer with different diffusion properties from that of the inner side of the film caused by differing distributions in molecular orientation or degrees of crystallinity.
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fountain flow for isothermal viscoelastic fluids is simulated by a numerical method based on a combination of a finite element method and a finite volume method. For the treatment of moving free surfaces, a fringe element generation method is used. Circulating flow and elongation in the transverse direction at the melt front are simulated well. Numerical results also suggest that circulation in fountain flow and viscoelastic retardation may give rise to symmetric V-shaped patterns of birefringence between the center-plane and wall. Such information on molecular orientation in fountain flow is important for physical properties of thick molded products.
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  • 29
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    Polymer Engineering and Science 35 (1995), S. 813-822 
    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: The effect of rigid particles on the fracture mode of polymers that yield with necking was analyzed theoretically with a model of regularly arrayed spherical particles. The adhesion between a polymer and particles was assumed to be weak, and particles were assumed to debond from the polymer before necking. A linear decrease in engineering draw stress with an increase in the filler content was derived. An increase in filler content leads to a transition in deformation mechanism. The transition depends on the ability of the polymer to strain-harden. If the ability to strain-harden is insignificant and the engineering fracture stress (strenght) of the polymer is lower than its yield stress, the transition is from ductile to brittle fracture. If the ability to strain-harden is essential and the strength of the unfilled polymer is higher than its yield stress, the transition (ductile-to-ductile) is from neck propagation to uniform ductile yield. The critical filler contents were determined for both transitions from the properties of an unfilled polymer. The ductile-to-ductile transition without embrittlement is possible if the strength of the unfilled polymer is higher than its yield stress. Results for polymers filled by weakly bonded particles were compared with polymers filled by particles that debond after the yield stress.
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  • 30
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    Polymer Engineering and Science 35 (1995), S. 823-836 
    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: An in-house-built and designed dilatometer was applied to the study of low profile unsaturated polyester resins. This article first describes the dilatometer used including its calibration then its application to low profile unsaturated polyester resins. Several series of dilatometry experiments were performed, to study the effect of low profile additive concentration and cure temperature on shrinkage control. Scanning electron micro-graphs of the samples were also prepared to show the correlation between shrinkage control and polymer morphology.
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  • 31
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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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  • 32
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    Polymer Engineering and Science 35 (1995), S. 1569-1579 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 self-wiping co-rotating twin-screw extruder was studied as a reactor for two polymerizations in bulk: the homopolymerization of n-butylmethacrylate and the copolymerization of n-butylmethacrylate with 2-hydroxypropylmethacrylate. The influence of the extrusion parameters on the product was analyzed. With both reactions, conversions up to 95% were obtained. Nevertheless, a significant difference was observed in the working domain of both polymerizations, in which a stable reactive extrusion process could be attained wherein the discharge rate is constant and equals the feed rate. In the case of the relatively fast copolymerization, both the throughput and the screw rotation rate could be raised without endangering the stability of the process. This was not the case for the homopolymerization studied. It was determined that the stability of the process depends on the reaction velocity and the product viscosity. Within the boundaries of the working domain, the molecular weight could be influenced by adjustments of the extrusion parameters.
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    Polymer Engineering and Science 35 (1995), S. 1581-1582 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 special issue is dedicated to the current and rapidly growing polymer research in Korea. The isue contains a grouping of typical research studies from Korea. The set is not inclusive, as there are many fine additional research programs under way in Korea. A brief history and comments on several aspects of Korean polymer research may provide a perspective.
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  • 34
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    Polymer Engineering and Science 35 (1995), S. 1583-1591 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Allylester prepolymers were synthesized by transesterification, and curing kinetics of alumina tihydrate reinforced allylester resins was studied by means of a differential scanning calorimetry dynamic experiment. The activation energies and the frequency factors of the reinforced allylester prepolymers were estimated by means of Ozawa's and Kissinger's methods. The values determined from the Ozawa method are higher than those from the Kissinger method. The peak exotherm temperature of reinforced allylester resin was shifted to a lower temperature as the concentration of curing agent increased. The peak exotherm temperature as the concentration of curing agent increased. The peak exotherm temperature of reinforced allylester resin was, however, shifted to a higher temperature as the content of alumina trihydrate increased. In the case of the dynamic experiment, both the activation energy and the frequency factor decreased as the concentration of curing agent was increased. Meanwhile, there exist minimum values of both the activation energy and th frequency factor with varying contents of alumina trihydrate.
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    Polymer Engineering and Science 35 (1995), S. 1600-1604 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 homopolymer of maleic anhydride was synthesized by free radical initiation and characterized. Molecular mass measurements of 14 selected fractions yielded Mw ranging from 1.1 × 104 to 14.7 × 104 g/ mol. Intrinsic viscosities obtained from the fractions in DME at 25°C were analyzed on the basis of the theory of Yamakawa et al. The persistence length was 2.3 ± 0.1 nm and ML was 600 ± 10 nm-1. The conformation of the poly(maleic anhydride) molecules in DMF is considered to be semiflexible.
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    Polymer Engineering and Science 35 (1995), S. 1592-1599 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na+ and ZN++) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.
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    Polymer Engineering and Science 35 (1995), S. 1605-1614 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 poly(butylene terephthalate) (PBT) with three different thermotropic liquid crystalline polyesters (TLCPs) were prepared. The first TLCP (HBH-6) consists of diad aromaticester type mesogenic units and the hexamethylene spacers along the main chain, and the second (TB-S6) is a wholly aromatic polyester TLCP having alkoxy side groups on the terephthaloyl moiety. The last (TR-4,6) is an LC copolymer comsisting of triad aromatic ester type mesogenic units and two differents spacers; tetramethylene and hexamethylene units. Blends of TLCP with PBT were melt spum at different LCP contents and differnt draw ratios to produce monofilaments. For the HBH-6/PBT and TB-S6/PBT blends, the ultimate tensile strength showed a maximum value at the 5 wt% level of LCP in the blends, and then it decreased when the LCP content was increased up to 20%. On the other hand, the initial modulus monotonically increased with increasing LCP content in all cases. The blends with TB-S6 showed the highest tensile properties of the three blends systems. This can be ascribed to the highest rigidity of the polymer chain, which still carries relatively long alkoxy substituents that promote sufficient adhesion between the LCP and PBT matrix. When compared with the PBT fiber itself, the fibers obtained from the 5% TB-S6/PBT blends exhibited an improvement in tensile strength by 〉 25% and in tensile modulus by ∼ 200%.
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    Polymer Engineering and Science 35 (1995), S. 1615-1620 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Transesterfication between a liquid crystalline polyster and poly(butylene terephthalate) was followed quantitatively by analyzing 13C-NMR spectra of the 50:50 blend after heat treatmetn at 290°C for varying lengths of time. Differential scanning nalysis was employed to follow the interchange reactions. From analysis of triad sequences of the transesterified blends, it was clear that measurable exchange reactions occurred when the blend was kept at 290°C for 20 min. The distribution of sequences tends to approach that of a statistical binary copolymer as the heat treatment period is increased. The results ontained from this investigation show that polyblends between an LC polyesterand conventional polyesters must be handled carefully. Otherwise, ester interchange reactions are inevitable.
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    Polymer Engineering and Science 35 (1995), S. 1621-1628 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study investigates deformation of a thermotropic liquid crystalline polymer (TLCP) in different die geometries. Blends of aTLCP with a thermiplastic elastomer of EPDM were made in a twin-screw extruder. Morphological observation of the extruded blends demonstrates the complimentary effect of shear in the die exit on dispersed phase deformation and fibril formation. Shear strain can affect fibril formation for a relatively large dispersed phase in the region close to the die wall. However, the main role of shearing is in breaking up the larger particles and initial polydomain structure. A strong elongational deformation on the blended melt after the die exit is required, and fine microfibrils normally obnserved in in situ composites were not easily formed by shear deformation only in the die.
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  • 40
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    Polymer Engineering and Science 35 (1995), S. 1629-1635 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Copoly(ehtylene terephthalate/imide)s (PETI) were prepared by melt polycodensation of bis(2-hydroxyethyl)terephthalate (BHET) and imide containing comonomer, 4,4′-bis[(4-carbo-2-hydroxyethoxy)phthalimido]diphenylmethane (BHEI) with Sb2O3 as catalyst at 280°C under vacuum (∼ 1 mm Hg). The change of Tm with an increase of the BHEI repeat unit in the PETI copolymer was analyzed by the Flory equation. On isothermal crystallization, a longer induction time and a lower activation energy than for the PET homopolymer were observed with an increasing amount of BHEI repeat unit. The Avrami exponent, n, increased from 1.5 to 2.3 as the content of BHEI or crystallization temperature was increased. The Avrami rate constant K decreased with the increase of the BHEL unit. On nonisothermal crystallization, the Ozawa equation and Lawton plot were used to investigate the effect of BHEI units on the crystallization kinetics of PETI copolymers. From the change of the cooling crystallization function and the result of the Lawton plot, it was found that the BHEI unit effectively decreases the rate of crystallization.
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    Polymer Engineering and Science 35 (1995), S. 261-273 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 plasticating screw extruder, a polymer melt forms in the melting zone of the extruder. Pressurization of the molten polymer takes place in the melting and the metering sections so that the melt can flow through the restricted passage of the die and assume a desired shape. In a melt fed extruder, the throughput is governed by the pressure rise over the entire length of the extruder. The pressure developed in the screw channel may also be employed in rapid filling of molds, such as those in injection molding. When the geometry of the screw, the barrel temperature, and the die are selected, a unique set of operating parameters arise for a particular flow rate or screw speed. In the present study, numerical and analytical methods are used to calculate the transport in the extruder and the pressure drop in the die. An iterative numerical method based on solving the equations of motion and energy in the screw channel and a correction scheme to couple the die with the screw channel is discussed. The numerical algorithm is capable of handling an arbitrary variation of the viscosity of the polymeric fluid with the shear rate and temperature. The results obtained by simulating the fluid flow in the screw channel are compared with available numerical and experimental results in the literature, indicating good agreement. The performance characteristics of the extruder, for chosen thermal boundary conditions and screw geometry, are presented for different die geometries and different fluids. The important considerations that arise in the numerical simulation of the extrusion process are also discussed.
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    Polymer Engineering and Science 35 (1995), S. 1725-1732 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 order to provide nw experimetnal facts required for constructing a nonlinear constitutive equationfor solid polymers, some tests wee conducted on amorphous pojymers of polycarbonate and poly(methyl methacrylate) and for a crystalline polymer of polyxymethylene under varous strain paths such as comprssion, torsion and combined tension-torsion. It is shown that (1) the stress-strain behavior for the strain paths without strain reversal is described well not only for amorphous polymers, but also for crystalline polymers by an overstess theory proposed by Krempl, and (2) at the strain paths wth stran reversal, the stress responses are considerably differetn from what is expected for the fstress responses of metals and their alloys.
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    Polymer Engineering and Science 35 (1995), S. 1733-1747 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The flow-induced and thermally induced residual stresses during injection molding of a thin part with complex geometries are predicted. The injection molding precess was considered to consist of a filling and a post-filling stage (packing coupled with cooling). Additionally, the analysis were applied to successive stages of the process. The model takes into account the viscoelasticity of the molding polymer, which has been neglected in most previous works, because of the complexity of its inclusion. A unified K-BKZ viscoelastic constitutive model, capable of modeling both the fluid-rubbery state and the glass state of amorphous polymers, was employed for simulating this problem. For the flow-induced residual stress predictions of the filling stage, a quasi-steady state approximation was employed for each element of the part, for the calculation of stress profile and subsequent stress relaxation after cessation of flowf. Stress calculations were provided for the thermally induced residual stress predictions of the post-filling stage. These explicit calculations led to the results of pressure and temperature distributions of the part during the post-filling stage into the viscoelastic constitutive model. Additionally, the pressure and asymmetric temeprature profiles of the post-filling stage were based on finite element packing analysis coupled with a boundary element cooling analysis of the molding process. Finally, the total residual stress in the part was obtained via superposition of the flow-induced and thermally induced residual stresses. An example is provided to demonstrate the entire concept. The results indicate that thermally induced residual stress is higher than the flow-induced residual stress by one to two orders of magnitude.
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    Polymer Engineering and Science 35 (1995), S. 1795-1806 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 torque rheometer method has been developed to evaluate the melt behavior of biopolyesters. The main features of this technique include: (i) a modified equipment configuration, so as to maintain the melt temperature within ± 1°C pf the set temperature after the first few minutes of polymer melting and thermal equilibration, and (ii) a kinetic equation that can be used to determine the melt behavior from the torque-time data. Applying this methology to a poly(3-hydroxybutyrate-co-3-hydroxyvalerte) copolymer shows that the degradation kinetics follow Arrhenius behavior with temperature, that the degradation rate increases with increasing hear, and that the activation energy for random chain scission is independent of shear rate. This effect of shear on the degradation process may be a result of viscous heating. The degradation rate is increased because of the increased internal energy of the polymer chains as a result of the mechanical deformation. There is no evidence of direct mechanical degradation. Last, the viscosity values obtained with the torque rheometer are consistent with those obtained by capillary rheometry.
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    Polymer Engineering and Science 35 (1995), S. 1785-1794 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 research addresses the wear properties and processes of 10 vol% polytetrafluoroethylene (PTFE) filled ultra-high molecular weight polyethylene (UHMWPE) composites and their relationship to mechanical properties. The addition of the PTFE micropowder results in a slight increase in modulus and a significantly lower strain at break. This is due to a quasi-brittle failure mechanism. Crosslinking the UHMWPE reduces both the modulus and the ultimate properties. Polymer wear studies against SiC abrasive paper can be divided into initial and steady-state processes. The initial wear, polymer-SiC wear, is dominated by microcutting and the formation of a transfer film. A single-pass wear rate (R1) can be derived from a power-law description of the initial wear. The steady-state wear eventually achieved, called polymer-film wear, is dominated by sliding against a self-generated. A steady-state multiple-pass wear rate (Rx) can be derived from a linear description of steady-state wear. The relationships between the wear of UHMWPE and the wear of PTFE can be predicted through their ultimate and deformation properties and through an understanding of the wear mechanisms. These relationships cannot be used to relate composite and UHMWPE wear due to their different failure mechanisms. The lower Rx and coefficient of friction of the composite may be related to the PTFE flakes found on the worn and wearing surface. Crosslinking the UHMWPE yields little change in the worn and wearing surfaces and in Rx. The increase in R1 on addition of PTFE and decrease in R1 on crosslinking may be related to the respective increase and decrease in modulus.
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    Polymer Engineering and Science 35 (1995), S. 1807-1810 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 prepared from poly(ethylene 2,6-naphthalate) (PEN) and poly(butylene 2,6-naphthalate) (PBN) show only partial miscibility judged from their glass transition temperatures. Two distinct mechanical behaviors are observed: brittle for the blends 〈 20 wt% of PBN, while ductile 〉 20 wt% of PBN. The experimental modulus and strength values of the blends are within the predicted values according to Kleiner and Paul models, respectively. This means that PEN/PBN blends are somewhat compatible based on their tensile properties. Especially for 20 wt% of PBN blend, the high modulus and strength are observed. The viscosity of the blend is high, which may imply a somewhat entangled morphology in the amorphous state.
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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 35 (1995), S. 1878-1883 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 LDPE/nylon-6 films with an overall content of 71 wt% LDPE, 24 wt% nylon-6, and 5 wt% PE-based tie-layer adhesive were reprocessed under both minimal and extensive mixing conditions. Thermal and mechanical properties, oxygen and water vapor permeability, and morphology of the reprocessed samples were determined. The modulus and yield stress of the reprocessed films fell between those of the pure homopolymers, whereas percent elongation at break and energy-to-break for all reprocessed films were less than those of the homopolymers. In minimally reprocessed film, layering of LDPE (low-density polyethylene) and nylon-6 was retained, whereas in extensively mixed samples, nylon-6 domains were spherical and ranged from 0.2 to 7 μm. Minimally reprocessed film exhibited good O2 and H2O vapor barrier properties, whereas extensively-mixed samples had poor barrier properties. Properties of well-mixed blends prepared both with and without adhesive showed that 5 wt% adhesive did not compatibilize the LDPE and nylon-6 components.
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    Polymer Engineering and Science 35 (1995), S. 1884-1894 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two series of unsaturated polyesters (UPE from isophthalic acid, fumaric acid, and propylene glycol) were prepared. In series-A resins, UPEs wee thickened with isocyanate-terminated saturated aliphatic polyestes, i.e., an isocyanate-terminated polycaprolactone diol (PE-di-OL), through reaction of the isocyanate group with the hydroxyl group of the UPE. In series-B resins, the UPEs were mixed with saturated aliphatic polyesters i.e., PE-di-OL. The curing reaction of these two series of UPEs with styrene was studied by using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The DSC data show that for a fixed PE-di-OL molecular weight, the curing reaction rate of series-A UPE is faster than that of series-B UPE. The variation of microgel size during curing ws studied by GPC. These results revealed that microgel formation has a great effect on the kinetics of cure for the unsaturated polyester-styrene system. The curing of these two series of UPEs is found to strongly depend on the compatibility of the components in the curing system.
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    Polymer Engineering and Science 35 (1995), S. 1895-1898 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 stress monitoring technique, a stress-tracking device, is described here. It has been used to study some important properties of epoxy resin. Residual stresses, including a curing shrinkage stress and a cooling shrinkage stress, were measured automatically and continuously during curing and cooling. Simultaneously, information such as an apparent gelation time and glass transition temperature were obtained directly during the experiment. These epoxy resin properties were related to the extent of cure. Varying cure temperature produced changes of cure behavior, which resulted in different residual stresses.
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    Polymer Engineering and Science 35 (1995), S. 1899-1906 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Processing of microcellular foam was investigated for the feasibility of production of tough and lightweight polyurethanes. To increase the nucleation rate in a gas-supersaturated resin, ultrasonic excitation was applied to the mixture of polyol(polyether-based polyol) and isocyanate(diphenyl methane diisocyanate). A microcellular structure was produced by two sequential steps, i.e., supersaturationof the polyol resin with nitrogen gas at elevated pressure and ultrasonic bubble nucleation right after the impingement mixing of two components of the polyurethane system. Theoretical analyses based on nucleation theories were employed to predict the rate of nucleation in the gas-supersaturated polyurethane. The rate of nucleatio in the resin was predicted by classical nucleation and cluster theories. In the experimental investigation, ultrasonic excitation was applied to increase the nucleation rate in the resin that had been saturated by nitrogen at a saturation pressure 〈 2.0 MPa.
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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 35 (1995), S. 1907-1916 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Previous research and this research indicate that the mechanical melting for poly(vinylidene chloride) copolymers (PVDC) is complex. Mechanical melting is defined as the melting (or devitrification) of a polymer when a significant portion of the thermal energy originates from a mechanical energy dissipative process. PVDC mechanically melted on a moving metal surface at temperatures of the test instrument that were considerably lower than the differential scanning calorimetry (DSC) onset melting temperature. PVDC formulated with low levels of high density polyethylene (HDPE), however, melted at metal temperatures near the DSC onset melting temperature. Two different mechanical melting mechanisms are proposed to explan the data, and the frictional data are discussed with respect to solids conveying in a single-screw, plasticating extruder.
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    Polymer Engineering and Science 35 (1995), S. 1917-1922 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polypropylene/Polyamide-6 (PP.PA) blends containing maleic anhydride grafted elastomers were prepared by reactive blending. Three different types of core shell morphologies were obtained and characterized by transmission electron microscopy (TEM). The midulus of these elastomer midified PP/PA (70/30) blends with core shell type morphology is compared to predictions derived from the Kerner model. The multiphase morphology of these blends could be modeled by sequential application of the Kerner equation to two-phase subinclusions. Using morphological data ontained by TEM, good agreement between experimental and calculated values was ontained. The results are used to tailor PP/Pa-6 blends combining stiffness and toughness.
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    Polymer Engineering and Science 35 (1995), S. 1231-1240 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Nylon 6 polymerization in batch reactors has been assumed to consist of important reactions of ring opening, step growth and polyaddition steps and a set of ordinary differential equations (initial value problem) for the concentrations and moments of the various reacting species has been derived. We have proposed a series solution for these variables in terms of conversion of ε-caprolactam. A technique similar to the finite element method for boundary value problems is used to divide the conversion domain into subdomains. The size of these is determined by a convergence criterion and the results determined at the end of conversion domain through sequential computations. This technique of solution involves the evaluation of constant coefficients of the series only and gives comparable results with those of Runge Kutta or Gear's algorithm (which involves evaluation of functions) in fewer steps. The scheme can easily be implemented on a personal computer and is considerably faster and more efficient.
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    Polymer Engineering and Science 35 (1995), S. 1252-1259 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 methodology to predict mechanical properties in injection molded parts has been developed. Knowledge of part properties before actual molding and testing will be of immense help to part and mold designers in modification of design. This methodology involved the application of connectionist learning systems, injection molding computer simulation, and experimental evaluation of mechanical properties, to relate the thermomechanical history of injection molded parts to the resulting part properties of injection molded parts are dependent upon their thermomechanical history which in turn is greatly influenced by the processing conditions and part geometry. As the relationships between engineering properties and thermomechanical history are complex and highly nonlinear, the methodology developed was based on a backpropagation neural network algorithm that provided the means for a nonparametric mapping between the part properties and thermomechanical history. The proposed methodology has been successfully applied to two geometries, plaque and box. This methodology provides designers with the ability to predict mechanical properties in injection molded parts when significant thermomechanical history can be obtained from injection molding simulation.
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    Polymer Engineering and Science 35 (1995), S. 1261-1271 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study clarifies and quantifies factors which increase the ductility of a low-molecular-weight propylene homopolymer having an intrinsic viscosity of 0.89 dl/g. The tensile behavior of homopolymer/ethylene-propylene rubber (EPR) blends was studied from the viewpoint of the associated molecular structure of EPR and its compatibility with the homopolymer. When EPR is “dissolved” in a homopolymer, the glass transition temperature (Tg) of the amorphous phase of a homopolymer was found to shift to a lower temperature, with homopolymer/EPR compatibility being subsequently evaluated using this shift, i.e., Δtg. Results show two conditions are required to improve the ductility of the low-molecular weight propylene homopolymer: ΔTg must be ≥ 3°C and ≥ 30 wt% EPR must be blended with the homopolymer.
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    Polymer Engineering and Science 35 (1995), S. 1272-1281 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 present study of resin transfer molding, an effective gap located between the side wall and the fiber mats is proposed. The concept of the effective gap leads to a permeable boundary condition on the interface between the fiber mats and the side wall. The porosity is no longer assumed to be a constant in the whole domain. Results show that the effective gap concept can explain the phenomena of edge effects reasonably. In our model, the filling process is simulated by the body-fitted finite element method and the limitation of the time increment for the quasi-steady state process is discussed in detail.
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    Polymer Engineering and Science 35 (1995), S. 1282-1289 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 creep behavior of polymers depends on the physical age of the material at the time of stress application. Creep curves shift to longer times for more highly aged material and, in poly(vinyl chloride), (PVC), this can be modeled by an empirical equation in which the magnitude of an effective mean retardation time parameter is dependent upon, and increases with, the age of the polymer. Creep compliances for PVC also depend on the magnitude of the applied stress when this exceeds about 4 MPa. This nonlinear behavior is caused, at short creep times, by a reduction in the value for the retardation time parameter on application of the creep stress. Specimens appear therefore to be initially de-aged by elevated stresses. Subsequently, this parameter increases with creep time implying that physical aging has been reactivated, but the rate of increase also depends on the stress level. These influences of elevated stresses can be described by an extension of the creep model, and parametric expressions have been derived which relate creep compliance values to time, stress, and the age of the polymer. It is shown how the parameters can be determined from a short series of creep experiments and thus how creep deformations can be calculated over wide ranges of time, stress, and age.
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    Polymer Engineering and Science 35 (1995), S. 1962-1971 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polypropylene (PP) composites containing 0.30 vol% of talc filler, in addtion to blends modified with an ethylene-propylene copolymer (EPR) elastomer were prepared and their fracture resistance was determined by the standard Ixod impact test and by a fracture mechanics technique. Effects of composition, type of modification, specimen size, and temperature were studied. The validity of linear elastic freacture mechanics (LEFM) conditions were checked: It was shown that under the conditions applied they can be satisfied even twith specimens of reasonable size (4 × 10 × 80 mm) prepared by conventional processing techniques. Calculations of minimum specimen thickness must be carried out, with material properties obtained under the conditions of impact. For heterogeneous blends and composites yield stress should be corrected for the effect of decreasing load-bearing cross section. Linearity of the fracture energy (U) vs. BDφ or U vs. B(D - a) plots is not a proof for either elastic of plastic fracture. The composition dependence of fracture properties proved to be practicaly independent of specimen size, temperature, or measurement technique.
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    Polymer Engineering and Science 35 (1995), S. 1972-1978 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 processing of high temperture thermoplastic polymers as a hot melt adhesive is one means of joining thermoplastics to metals. The presetn study establishes the role of processing in thermoplastic joining of a titanium alloy (Ti-6A1-4V) using thin flim poly(etherketoneetherketoneketone) (PEKEKK). A design of expriments (DOE) was performed to determine the effects of the soak above melt temperature (Tm = 380°C), hold at the isothermal recrystallizztion temeprature (Tiso = ∼ 340°C) and cooling rates on the joint strength, Extended soak times are required to remove the residual spherulitic crystallinity in the polymeric adhesive. Whit the elimination of the residual crystallinity, high-strength transcrystalline regions are enhanced at the polymer-metal interface during the hold time at Tiso and during cooling to ambient temperature. Average tensile strengths of 137 MPa were achieved, exceeding the bulk polymer tensile strength of 118 MPa by 16%, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) show that extended soak times above Tm led to excessive polymer squeeze-out, resulting int he creation of strength-reducing shrink voids or unwetted regions. As a result, the failue mode of the joint, which was normally cohesive for high-strength joints, became a mix of cohesive and adhesive in parts with excessive polymer squeeze out.
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  • 62
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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: Recent work on the determination of residual stress in drawn pipes has revealed an error in previous methods used. Such pipes have residual stresses very different from those induced by melt extrusin during conventional pipe processing. In particular, it appears that there are considerable compressive stresses at the bore, and the hoop and axial values are not equal. In an attempt to measure these values, tests were performed on slit rings of varying length, and a pronounced dependence of ring overlap on length was observed. This was contrary to previous assumptions, and a corrected version of the analysis has been developed, which enables the true hoop and axial stresses to be determined by testing rings of various lengths. For isotropic pipes, it has been shown that hoop and axial stresses are roughly equal. Previous results obtained on thin pipe rings can now be corrected by multiplying by the factor 1/(1-v). For anisotropic drawn pipes, a combination of rings and thin axial strips is used to determine the residual stresses. These pipes can show remarkably low stresses at the bore, which may play a significant part in determining their performance.
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    Polymer Engineering and Science 35 (1995), S. 1394-1406 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 viscoelastic behavior of acrylonitrile-butadiene-styrene (ABS) terpolymers is studied in the molten state. First, the behavior of the styrene-acrylonitrile (SAN) matrix is determined. Then, the effect of the degree of grafting on ABS rheological properties is emphasized. A critical degree of grafting (DGc), corresponding to a minimum of the viscoelastic functions in the low frequency region, is determined. It defines a critical thickness of the grafted layer, and is related to the conformation of the grafted chains at the surface of the rubber particle. The DGc affects the morphology of the ABS and also affects the appearance of a secondary plateau at low frequencies. The effects of the rubber particles, of the grafted chains, and of the morphology on the appearance of the secondary plateau at low frequencies are clearly dissociated.
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    Polymer Engineering and Science 35 (1995), S. 1407-1412 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 sodium salts of carboxylic acids and other weak acids are routinely used as nucleation agents for injection moldable poly(ethylene terephthalate) (PET) resins. One of the primary drawbacks accompanying their use is the degradation of the PET resulting from the attack of the ester by the sodium carboxylate. Several sodium carboxylates have been found based on pyrrole carboxylic acid that are effective as nucleants but which do not cause a reduction in the molecular weight of PET. In addition, tetraphenyl borate salts, although only marginally effective as nucleants, were observed to be efficient additives to PET for counteracting molecular weight loss caused by chemical nucleants.
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    Polymer Engineering and Science 35 (1995), S. 1413-1417 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 NMR (nuclear magnetic resonance) and GPC (gel permeation chromatography) studies of the polymerization of maleic anhydride and 1,2-propylen glycol are reported. Assignment of individual groups was made and their concentration dependence on reaction time was established. The first step of the reaction is the formation of monoesters, which, immediately after the temperature increased, reacted to diesters. The reactivity ratio between the primary and the secondary hydroxyl group of 1,2-propylene glycol was 2.6:1. The concentration of water formed was followed as a function of reaction time by the Karl-Fischer method.
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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 35 (1995), S. 1421-1432 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the Tg and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.
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    Polymer Engineering and Science 35 (1995), S. 79-91 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: During the last few years, improvements in control strategies became a necessity, with controls being targeted on material properties. The ever-increasing demand for polymer blends spells the need for in-line instrumentation capable of monitoring blend properties such as morphology. Since ultrasonics have proved to be sensitive to properties of multiphase materials, their performance for discriminating blend morphology was explored here. In-line and off-line (static, with no flow) ultrasonic measurements were made on different blends of polystyrene (PS), polyethylene (PE), and polypropylene (PP) for various viscosity ratios, and over the entire range of composition. Blends were compounded on a ZSK-30 Werner & Pfleiderer intermeshing co-rotating twin-screw extruder. In-line ultrasonic measurements were performed on both single-screw and twin-screw extruders. Ultrasonic properties (velocity and attenuation) were found to vary approximately linearly with composition. Mixing rules were evaluated for the description of ultrasonic behavior. For the attenuation measurements, the positive deviations from these rules were found significant. The additional attenuation was attributed to scattering generated by the presence of the minor phase inclusions.
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    Polymer Engineering and Science 35 (1995), S. 92-99 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 phase behavior of polymer blends under simple shear flow has been studied using a custom-designed rheo-optical system consisting of a two-dimensional small-angle light scattering (SALS) device incorporated into a conventional rheometer. Two-dimensional SALS images were gathered for model polymer blend systems with different quiescent phase behavior: polystyrene/polyisobutylene (PS/PIB) that exhibits upper critical solution temperature phase behavior and polystyrene/poly(vinyl methyl ether) (PS/PVME) that shows lower critical solution temperature phase behavior. For the PS/PIB blend, shear-induced phase mixing occurred at a critical shear rate. Below that critical shear rate, the dispersed phase was highly elongated parallel to the flow direction. For PS/PVME blends, a streak scattering pattern was observed even though the sample became optically clear after shearing. We observed, apparently for the first time, the development of a bright-streak pattern from a transient dark-streak pattern for a polymer blend system under shear. Rheo-microscopy studies revealed an intriguing wave pattern that developed coincident with the observation of a streak pattern by SALS. The relationship between the two phenomena has not yet been established.
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    Polymer Engineering and Science 35 (1995), S. 115-127 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 Part II of this series of publications, the first generation model of morphology evolution during polymer blending in a twin-screw extruder was presented. The model was based on a simplified flow analysis, and an assumption that dispersion occurs via drop fibrillation followed by disintegration. In the present Part IV, several modifications of the model are discussed. (i) The flow analysis was refined by computing the pressure profiles. (ii) The flow paths and strain history of the dispersed droplets within the screw elements are computed directly, which makes it possible to determine the drop susceptibility to deformation and break. (iii) Besides the fibrillation mechanism, a drop-splitting mechanism for low supercritical capillary numbers is incorporated. (iv) The choice of breakup mechanism is based on micro-rheological criteria. (v) The coalescence effects are taken into account. (vi) The theoretical model is self-consistent, without adjustable parameters. The validity of theoretical assumptions was evaluated by comparing the model predictions with the experimental droplet diameters at different positions in the twin-screw extruder.
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    Source: Wiley 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 dispersions of both reactive and nonreactive polymer-polymer blend systems achieved in three different mixers are compared. The dispersions are prepared using an industrial scale twin-screw extruder, a laboratory internal mixer, and a miniature cup and rotor mixer. The morphology development in the three mixers is remarkably similar: The dispersed phase is stretched into sheets and ribbons; these sheets and ribbons then break into cylinders, which subsequently break into droplets via Rayleigh-type instabilities. Drop size distributions can be accurately predicted if we know the size of cylinders formed in the high shear fields of the mixer. There is a significant effect of quenching time on blend morphology - i.e, to properly evaluate mixing, blends must be quenched extremely quickly (well within a minute). Otherwise, we need to consider the morphology development during the quenching time, which may not be relevant to the mixing. There is a uniform shear stress in the miniature mixer, unlike the other mixers, which have varying stress levels. It is shown that a high stress level followed by a lower stress level is required in polymer blending to achieve efficient mixing. In the high stress level, the dispersed phase is stretched into extended shapes, which undergo instabilities and break up upon entering the low stress level. In the miniature mixer, the dispersed phase sees only one stress level, and thus very extended shapes persist at the end of mixing. The final dispersions in the twinscrew extruder and internal mixer at matched maximum shear rates are almost identical. For similar shear rates in the miniature mixer, the final dispersion of reactive blends is comparable to the other mixers. However, the miniature mixer does a poor job in dispersing high viscosity uncompatibilized blends, and the mixing conditions must be altered to obtain efficient mixing.
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  • 72
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    Polymer Engineering and Science 35 (1995), S. 538-545 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.
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  • 73
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    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: 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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  • 74
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    Polymer Engineering and Science 35 (1995), S. 557-563 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The coefficient of dynamic friction is often the controlling factor for solids conveying, pressure generation, and thermal decomposition of a resin in the feed section of a single-screw plasticating extruder. The coefficients of friction are, however, very poorly understood, and the interpretation of the measurements are complicated by the dissipation of frictional energy at the sliding interface. A new instrument was recently built to help understand dynamic friction, and a numerical technique was developed to estimate the interface temperture. Coefficients of dynamic friction for several polyethylene resins are presented in this paper as a function of the surface temperature, pressure, and velocity. The relationship of the data with respect to the extrusion process is discussed.
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  • 75
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    Polymer Engineering and Science 35 (1995), S. 564-576 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Reaction injection molding of amine terminated butadiene acrylonitrile copolymer (ATBN) modified epoxy resin was investigated through computer simulation and experiment. The epoxy system composed of diglycidyl ether of bisphenol A (DGEBA) and triethylene tetramine (TETA) was employed since this system indicated a relatively high reaction rate. The coupled balance equations of momentum, chemical species, and energy within the disc-type mold cavity were solved using finite difference techniques. The predicted temperature and conversion profiles within the mold were compared to experimental results. The domain correlation length data calculated from the simulation model were compared with the results of SEM micrographs. A moldability analysis was performed to find the optimum molding conditions. The moldability window decreased as the mold thickness was increased.
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  • 76
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    Polymer Engineering and Science 35 (1995), S. 577-586 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 one-dimensional flow model for non-Newtonian liquids inside a dual-cavity slot die is presented. The model is capable of analyzing slot dies of any cavity shape, cavity taper, slot-length variations, and slot-gap variations. The proposed model incorporates a truncated-power-law model for the viscosity of non-Newtonian liquids. According to flow models with power-law approximation for liquid viscosity, the distribution of non-Newtonian liquid through a slot die depends on the slot Reynolds number only. With our model, we find that the zero shear viscosity and the relaxation time of a non-Newtonian liquid have large effects on its distribution. For non-Newtonian liquids which are expected to experience shear-thinning over portion of a slot die, it is concluded that a flow model with a truncated-power-law approximation for liquid viscosity be used to predict the liquid distribution from the die.
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  • 77
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    Polymer Engineering and Science 35 (1995), S. 1098-1105 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Evaporation behavior of water/solvent blends was estimated using the universal functional activity coefficient, UNIFAC, method. The evaporation rate from a free surface of a waterborne coating, WBC, containing a co-solvent was experimentally determined. These results were used to estimate the evaporation rate from wet films of a WBC containing a variety of co-solvents with a range of initial thickness. Knowing the composition of the WBC during the drying process, the change in the viscosity and the surface tension was determined. The results strongly support the development of a surface tension gradient in the film. It is also suggested that a surface tension gradient would accelerate the leveling of the ribs if a proper co-solvent were employed.
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  • 78
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    Polymer Engineering and Science 35 (1995), S. 598-603 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 deals with the residence time distribution (RTD) in a non-intermeshing counter rotating twin screw extruder.The RTDs were measured in three vent zones of the extruder sparately, and in the adjacent zones combined, using a soluble dye as the tracer. Assuming that the RTDs in the adjacent zones are independent of each other, the overall RTD was also calculated using a previously developed statistical theory. The theory has also confirmed the consistency of the present measurements.A predictive RTD model for the non-intermeshing twin screw extruder, based on the flow analysis of the individual screw zones and their statistical superposition, was also developed. The predictions are in good agreement with experiment.
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  • 79
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    Polymer Engineering and Science 35 (1995), S. 165-169 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of physical aging on the failure behavior of a typical brittle polymer, polystyrene, have been studied. Properties examined were creep rupture lifetimes, fatigue lifetimes, and environmental stress cracking in ethanol. Fractured samples were examined both optically and by scanning electron microscopy to determine the degree of crazing. It was found that a longer physical aging time produced shorter lifetimes in all cases. The main reason for this is the reduction in craze strength caused by a reduced toughness due to physical aging. A long aging time was found to delay craze formation, but once formed, these crazes were much less stable than those formed with a short aging time. The effects of aging are important on failure prediction criteria and on testing methodologies, and the implications are discussed.
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  • 80
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 orientational drawing of films from different thermoplastics has been studied. The value of the activation energy of drawing in the regions of forced elasticity (necking), high elasticity, and viscous flow (ΔE1, ΔE2, ΔE3) has been found to vary directly with the activation energy for viscous flow of the melt (ΔEη). Here ΔE1 〈 ΔE2 〈 ΔE3 = ΔEη. Thus Δ Eη characterizes the potential of thermoplastics for orientational drawing under different deformation conditions, since it reflects simultaneously both the intermolecular interaction level and chain flexibility. For maximum chain orientation, the calculated values for the change in the entropy are close to that of the entropy change during crystallization (melting) of the same polymer. The deformation of polymer may be described as a deformation of an entanglement network from the standpoint of classic elasticity theory. Some parameters for an entanglement network were calculated from the results of the drawing experiments. The density of the entanglement network (DEN) depend on the polymer composition: For flexible-chain polymers the DEN is less, for rigid-chain polymers (with coiled chains) it is higher. The DEN affects the maximum (prebreak) drawing ratio: The greater the DEN, the smaller the ratio to which a film can be drawn. At high orientation, the tensile strength of different polymer films tend to be similar, if drawing is not accompanied by crazing.
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  • 81
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    Polymer Engineering and Science 35 (1995), S. 180-183 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Halogenophenol novolac (HPN)-based negative resists exhibit excellent sensitivity and pattern resolution properties. The HPNs act as synergists for crosslinking with other irradiation labile compounds such as naphthoquinone diazide and bisazide vs. hydrogen halide (HX) elimination reaction, resulting in additional crosslinking, probably by aryl radical recombination and/or addition. We describe a new resist formulation based on HPN binder and melamine crosslinker (Cymel 303). In this case the irradiation induced HX elimination additionally catalyzes the melamine crosslinking.
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  • 82
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    Polymer Engineering and Science 35 (1995), S. 184-189 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dielectric and rheological measurements are reported for the cure in a series of mixtures of an epoxy-acrylate with n-butyl methacrylate. The level of the initiator and properties of the epoxy acrylate and n-butyl methacrylate influence the cure characteristics and morphology of the film formed. Analysis of the rheological data indicates that during the curing process, microphase separation occurs within the mixture. The changes in the dielectric relaxation behavior with composition of the completely cured material is also consistent with microphase separation occurring in these resins while they are cured.
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    Polymer Engineering and Science 35 (1995), S. 190-194 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 block copolyetheresters with hard segments of poly(butylene terephthalate) and soft segments of poly(tetramethylene ether) were prepared by a terephthalic acid (TPA) process in the presence of some salts. The preparations of a block copolyetherester under various conditions were first studied in a 1 L stainless steel reactor to find the best method. Then, the preparations of four block copolyetheresters were run in a pilot plant comprising a 200 L polyesterification reactor and a 200 L polymerization reactor under the suitable condition. The presence of some salts reduced the formation of tetrahydrofuran (THF), and also reduced the total reaction time in the pilot plant. The thermal properties and various mechanical properties of the block copolytheresters prepared by the pilot plant were investigated to evaluate the feasibility of this method.
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  • 84
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    Polymer Engineering and Science 35 (1995), S. 1191-1195 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Extruded microlayer sheets of Polycarbonate/Polyester (PC/PCTG) and Polycarbonate/Styrene-acrylonitrile (PC/SAN) were tested for ballistic performance. Composition of the microlayer sheets ranged from 60 to 100 percent polycarbonate. The number of layers in the approximately 3 mm thick sheets ranged from on for the blend control samples to 3713 layers in the PC/PCTG sheets. The normalized ballistic test results showed that some samples performed as well as as and slightly better than injection molded polycarbonate samples. The failure mechanism was affected by the composition and the number of layers. Increasing composition of polycarbonate and number of layers decreased the percent of brittle failures.
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  • 85
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    Polymer Engineering and Science 35 (1995), S. 797-804 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Recently, a model was developed for the nonisothermal crystallization of normal alkanes with chain lengths between 30 and 50. The model was derived based on the fundamental equation of Ozawa for nonisothermal crystallization, the surface nucleation theory, and the growth rate theory for extended chain crystals. In this paper, the proposed model is modified and extended to the case of polymer crystallization. Experimental differential scanning calorimetry data for three isotactic polypropylene resins with different molecular weights are presented at five cooling rates from 2 to 40 K/min. Model predictions are in excellent agreement with the experimental data for the three polymers at low and high supercoolings.
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    Polymer Engineering and Science 35 (1995), S. 786-793 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method to determine viscoelastic changes in medium density polyethylene (MDPE) pipe specimens associated with the crack tip during fatigue crack initiation (FCI) and propagation (FCP) experiments is described. The load-displacement curves are analyzed to obtain the phase angle, δ. Changes in δ are related to the number of cycles of crack initiation of three different MDPE copolymers: hexene (H), butene (B), and methyl pentene (MP) copolymers. These changes are related to craze formation and growth at the notch tip, leading to crack initiation and to the irreversible work, Wi, expended on them. Within a given material, step wise increments in δ distinguish the onset of crack initiation and the brittle-to-ductile transition in crack growth. The magnitudes of tan δ and Wi are noted to be in quantitative agreement with the resistance of the three copolymers to FCI and brittle propagation that rank in the order: isobutyl (MP) 〉 ethyl (B) 〉 butyl (H). Similar crystallinity of the three copolymers insinuates a hypothesis that variance in the nature of chain entanglements associated with the respective branch type might be accountable for the observed differences in viscoelastic character. The final stage of failure by ductile tearing is dominated by large scale plastic flow that seemingly overshadows the material differences governing time dependent brittle fracture.
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    Polymer Engineering and Science 35 (1995), S. 1979-1984 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 rheological behavior of multilayer polyjeric structures has been investigated Measurements of the bulk viscoelastic properties via small-amplitude oscilatory rheometry indicated that the shear viscosity is independent of both the numbe of layers (83 vs. 165) and the composition (30/70, 50/50, and 70/30 PC/PMMA by weight) within the limits of the data obtained. It is also apparent tha tthe shear viscosity is influenced strongly by the skin layer material. In additon, a model has been developed tha tcan be used to proedict the shear viscosity and shear stress ofa multilayer structure experiencing shear flow. The model predicts tha thte shear viscosity of a multilayer structure should be independent of the number of layers and strongly dependent on the material in the skin layer. These predictions are in agreement with experimental data.
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    Polymer Engineering and Science 35 (1995), S. 877-892 
    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: Isothermal experiments on gas-assisted displacement of viscoplastic liquids in tubes show that a liquid coating remains on the tube wall. The thickness of this coating approaches 0.35 of the tube radius at high gas penetration rates, the asymptotic limit previously observed for Newtonian liquids. At low gas penetration rates, the viscoplastic coating is much thinner than its Newtonian counterpart. During the displacement process, the gas front moves faster than the liquid front and, prior to blowout, it rapidly accelerates as the amount of liquid downstream of the gas is depleted by the liquid coating. Based on these observations, a simple isothermal model is developed to describe the gas-liquid dynamics. This model provides an insight into the gas-assisted injection molding process in which the injection of molten plastic into a mold is assisted by a pressurized gas. In particular, the results show that the wall thickness around the hollow cores in gas-assisted parts is set during processing by the solid skin and a thick molten layer. The thickness of the molten layer depends on the gas penetration rate and the viscous behavior of the molten plastic. By coupling the isothermal model with a one-dimensional heat-transfer analysis, the gas penetration rate is shown to be several orders of magnitude higher than the plastic freezing rate, so that most of the heat transfer between the melt and the gas occurs after the mold is filled.
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    Polymer Engineering and Science 35 (1995), S. 893-901 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Presence of weldlines introduces an element of uncertainty to the performance of injection molded parts. Weldlines are particularly problematic in reinforced plastics because, unlike molecular orientation in neat polymers, the flow induced fiber orientation does not relax. This paper deals with the structure and mechanical behavior of weldlines in glass fiber reinforced nylon 66, a plastic known for excellent fiber-matrix adhesion. Two molds were used to generate weldlines: a double gated tensile sample shaped cavity in which the weldline is formed by a head-on collision of melt fronts flowing in opposite directions and a film gated rectangular plaque with a circular insert in which the weldline formation behind the insert is followed by additional flow. In both cases the weldline zone is several millimetres wide: in the plane where the melts fronts have met fibers are oriented parallel to this plane (random-in-plane in the double-gated cavity and unidirectional in the cavity with insert). The transition zone between the weldline plane and the rest of the sample is characterized by an increased presence of microvoids. Weldline tensile depends little on the fiber concentration and on the sample shape or thickness: values close to the matrix strength are found: in samples without weldlines strength increases with the fiber content. However, in instrumented impact penetration test during which the material is subjected to multiaxial loading, the weldline effect appears negligible.
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    Polymer Engineering and Science 35 (1995), S. 902-910 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Wide angle X-ray diffraction pole figure, small angle X-ray scattering (SAXS), and refractive index techniques have been employed to investigate structure and deformation mechanisms in unidirectionally cold-rolled ultrahigh molecular weight polypropylene (UHMWPP) films. All reciprocal lattice vectors (plane normals) of (110), (040), and (130) were found to populate in the film normal (thickness) direction, suggesting that more than one orientation process must be involved in the deformation. SAXS studies on the cold-rolled UHMWPP reveal an oriented lamellar structure with its long axis perpendicular to the rolled direction, however, the lamellae are somewhat tilted. Refractive index and tensile measurements were undertaken to determine the optical and mechanical anisotropy of the cold-rolled UHMWPP films. A similar study was undertaken of unidirectionally rolled conventional polypropylene (PP) for comparison.
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    Polymer Engineering and Science 35 (1995), S. 284-288 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 dielectric relaxation of unsaturated polyester resin during cure was modeled using a modified Williams-Watts decay function. The dielectric response was studied using dielectric measurements coupled with two dynamic mechanical measurement methods. It was found that the variation of the relaxation time during cure is a WLF process using Tg (α) (α-conversion) as the varied temperature. It was shown that this process fits the Williams-Watts decay function Φ(t)=exp(-(t/τ)β) where τ-relaxation time and β-empirical parameter are time dependent. It was found that τ obeys a time dependent power law rule and β depends linearly on log(time). Using this modified decay function, it was shown that the experimental dielectric response measured during cure agrees well with the computed response. Relaxation times above and below the dielectric measurement system capability were computed thus, demonstrating the capability of yielding the entire relaxation times spectrum during cure, out of a single limited frequency dielectric measurement.
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    Polymer Engineering and Science 35 (1995), S. 274-283 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: It is of great importance in designing extruders to predict the screw characteristics, that is, the throughput in terms of the screw speed and the pressure gradient along the down-channel direction. The screw characteristics depend on the extruder geometry, the operating conditions, and material properties of non-Newtonian fluids. This paper suggests a simple approach to determining the screw characteristics for a three-dimensional flow in a channel with a finite aspect ratio (ratio of a width to a depth, W/H) by introducing a Total Shape Factor (Ft) to correct a two-dimensional flow analysis for a channel with an infinite aspect ratio. In the present study, the Total Shape Factor (Ft) was defined as a ratio of a net flow rate obtained by the three-dimensional analysis to that by the two-dimensional analysis. In the proposed approach, the quantity, ∂Ft/∂(H/W), which turns out to be almost constant, offers important information for understanding the effects of the flights. Threfore, ∂Ft/∂(H/W) is extensively reported in this paper in terms of several dimensionless parameters. This simple approach with such a database will be very useful for extruder designers to predict screw characteristics.
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    Polymer Engineering and Science 35 (1995), S. 1643-1651 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 morphology and dynamic mechanical properties of blends of poly(ether imide) (PEI) and nylon 66 over the full composition range have been invesigated. Torque changes during mixing were also measured. Lowertorque values than those calculated by the log-additivity rule were ontained, resulting from the slip at the interface due to low interaction between the componeents. The particle size of the dispersed phase and morphology of the blends were examined by scanning electron microscopy. The composition of each phase was calculated. The blends of PEI and nylon 66 showed phase-seoarated structures with small spherical domains of 0.3 ∼ 0.7 μm. The glass transition temperatures (Tgg) of the blends were shifted inward, compared with those of the homopolymers, which implied that the blends were partially imiscible over a range of compositions. Tg1, corresponding to nylon 66-rich phase. This indicated that the fraction of PEI mixed into nylon 66-rich phase increased with decreasing PEI content and that nylon 66 was rerely mixed into the PEI-rich phase. The effect of composition of the secondary relaxations was examined. Both Tβ, corresponding to the motion of amide groups in nylon 66. and Tγ′, corresponding to that of either groups in PEI, were shifted to higher temperature, probably because of the formation of intermolecular interactions between the components.
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  • 94
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1661-1669 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Recently, Friedrich proposed an empirical model for linear viscoelastic fluids corresponding to a constitutive equation with fractional derivatives [Phil. Mag. Lett., 66, 287 (1992)]. For this model, the relaxation modulus, the dynamic moduli, the relaxation time spectrum, and other material functions have been explicitly calculated as a function of the few parameters that characterize a viscoelastic fluid within this model. By fitting this model to experimental data, the model parameters can be determined and other material functions, in particular the relaxation time spectrum, can be calculated immediately. This paper reports to what extent this method, which may be called analytical inversion, is appropriate for the determination of relaxation time spectra. For that pupose, the spectra of a number of very different polymeric materials are determined with this method. The spectra calculated in this way are compared with the spectra obtained by nonlinear regularization. It turns out that the empirical model describes the linear viscoelastic properties of a variety of different materials with high accuracy. Keeping in mind that the determination of the relaxation time spectrum requires the solution of an ill-posed problem, the agreement between the relaxation time spectra obtained by analytical inversion and by regularization is satisfactory for these materials.
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  • 95
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1670-1681 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rheometric data for short-fiber-filled thermoplastics are presented using a parallel-plate viscometer. Polypropylene tensile bars contain short and long fibers with glass weight percentages of 0%, 5%, 10%, 20%, and 30%, polycarbonate tensile bars with glass percentages of 0%, 5%, and 10% long fibers, and nylon 6/6 tensile bars with 0%, 15%, 30%, and 45% short fibers. The short fibers were initially 3 mm in length and 12.7 microns in diameter. The long fibers were initially 6 mm in length and 10 microns in diameter. In the steady-state experiments, the fibers increase the viscous stresses and the normal stresses in proportion to the concentration of fibers. At low shear rates, the viscosity is increased by the addition of the fibers, but at high shear rates the viscosity approaches that of the neat resin. In dynamic testing, the fibers increase the viscous and elastic components as measured by the complex viscosity and modulus. The fibers increase the viscous and elastic nature of the fiber-filled composite at low frequencies and to a lesser extent at higher frequencies. The fibers increase the elastic component more than the viscous component at low frequencies and less at higher frequencies as demonstrated by tan δ.
    Additional Material: 29 Ill.
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  • 96
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1688-1694 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study reports on the progression of processes occurring in polymer blends during mixing. For the polymer pellet blends studied, an abrupt phase inversion was observed simultaneous with attainment of maximum torque in the batch mixer. A four-step phase inversion mechanism is described as predominant where dissipative mix-melting of the polymer system occurred in the mixing process.
    Additional Material: 10 Ill.
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  • 97
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 310-316 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Displacement controlled experiments on nylon 66, poly(etherether ketone), and poly(ether imide) at room temperature suggest that nonlinear elastcity is not a good model for these polymers. Rather, qualitative evidence is presented that a state variable model shows promise. In this model, the rate of deformation is the sum of the elastic and the inelastic rates of deformation. The elastic rate of deformation is given by an objective formulation of Hooke's law, and the inelastic deformation is an increasing function of the overstress, the difference between the Cauchy stress and the equilibrium stress. The equilibrium stress is a state variable, and represents the stress that can be sustained at rest following deformation. Load controlled tests, intended to verify or falsify the model, show that the creep rate at the same stress level can be different on loading and unloading, and that the creep rate need not increase with an increase in creep stress level. These anomalous results can easily be explained by the introduction of the overstress concept, and by proper evolution of the equilibrium stress. They confirm the usefulness of the overstress concept for the modeling of these polymers.
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  • 98
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1695-1704 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four isotropic polymers, poly(butylene terephthalate) (PBT), polycarbonate (PC), polyethersulfone (PES) and polysulfone (PSU), were blended by extrusion with a thermotropic liquid crystalline polymer (LCP) at different temperatures. The morphology of extrudates was observed by means of scanning electron microscopy and the intrinsic aspect ratio of LCP fibrils and particles separated from matrix resin was measured with an image analysis. Special attention was paid to the LCP fibrillation in these four matrices in a wide temperature range from 270 to 360°C and the internal relations among the effects of processing parameters, such as viscosity ratio, extrusion temperature, and LCP concentration. The results show that the viscosity ratio of the dispersed LCP phase to the continuous phase is a decisive factor determining the formation of LCP fibrils, but its effect closely relates with the LCP content. In the range of viscosity ratios investigated, 0.004 to 6.9, and lower LCP content of 10%, significant fibrillation took place only at viscosity ratios below 0.01. It is predicted that the upper limit of the viscosity ratio for LCP fibrillation will increase with increasing LCP content. A comparison of the morphologies of LCP/PES blends with different LCP concentrations reveals that the LCP phase becomes continuous at a concentration of less than 50%, and high LCP content does not always favor the formation of long and uniform LCP fibrils. The extrusion temperature has a marked effect on the size of the minor LCP domains. For fibril forming systems, the percentage of LCP fibrils with larger aspect ratios increases with increasing extrusion temperatures. All these results are explained by the combined role of deformation and coalescence of the LCP disperesed phase in the blend.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 331-344 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two features of the glassy state of an amorphous polymer, which play a key role in determining its mechanical properties, are the distributed nature of the microstructural state and the thermally activated (temporal) evolution of this state. In this work, we have sought to capture these features in a mechanistically motivated constitutive model by considering a distribution in the activation energy barrier to deformation in a thermally activated model of the deformation process. We thus model what is traditionally termed the nonlinear viscoelastic behavior as an elastic-inelastic transition, where the energetically distributed nature of inelastic events and their evolution with straining is taken into account. The thermoreversible nature of inelastic deformation is modeled by invoking the notion of strain energy stored by localized inelastic shear transformations. The model results are compared to experimental data for constant true strain rate uniaxial compression tests (nonmonotonic) at different rates and temperatures; its predictive capabilities are further tested by comparison with compressive creep tests at different stress levels and temperatures.
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  • 100
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 345-350 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 constitutive equation for nonlinear viscoelasticity is used to model the mechanical response of solid polymers such as polycarbonate. The nonlinearity arises from a reduced time which causes stress relaxation to accelerate with increasing strain. The constitutive equation can account for the occurrence of yield in a homogeneous uniaxial constant strain rate test. The constitutive equation is used in a study of the pure bending of beams. It is assumed that the classical assumption of beam theory is valid, i.e., plane sections remains plane. At each fixed time, the strains vary linearly through the depth of the beam. At a fixed material element the strain varies in time with the curvature. This spatial variation of the strains combined with the nonlinear dependence of the reduced time on strain leads to a significantly different response from that given by traditional beam theory. The implications of this for the bending moment history, stress distributions, and other factors that relate to beam design are discussed.
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