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  • Articles  (5,554)
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  • glass transition  (53)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Advanced Materials for Optics and Electronics 8 (1998), S. 77-80 
    ISSN: 1057-9257
    Keywords: conducting polymers ; polypyrrole ; electrical conductivity ; pressure ; conformation ; glass transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: We describe the observation of a pressure-induced variation in the electrical conductivity of BF-4-doped polypyrrole at pressures below atmospheric pressure. We also show that there are anomalies in the temperature dependence of the electrical conductivity in cyclic measurements at temperatures of 240 and 310 K. The pressure effect is interpreted as a pressure-induced order-disorder conformational transition. The anomalies in the temperature dependence are attributed to the glass transition and melting of the polymer. © 1998 John Wiley & Sons, Ltd.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2461-2470 
    ISSN: 0887-6266
    Keywords: dielectric relaxation spectroscopy ; thermosets ; interpenetrating polymer networks ; curing reaction ; temperature-modulated differential scanning calorimetry ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation spectroscopy (3 kHz ≤ ƒ ≤ 3 MHz), differential scanning calorimetry, and temperature-modulated calorimetry have been performed during isothermal curing of an epoxy network (diglycidylether of bisphenol A crosslinked with diaminodiphenyl methane), and of two thermoplast modified epoxy resins (semi-interpenetrating polymer networks) consisting of the epoxy network component and different amounts (10 and 20 wt %) of a linear high Tg polymer (polysulfone or polyethersulfone). During reaction, the homogeneous-mixtures phase separate into an epoxy-rich and a linear polymer-rich phase with different mobilities of the electrical dipoles. The complex dielectric permittivity is composed of a contribution from the ionic dc-conductivity and a contribution from relaxations of the permanent electrical dipoles in the two phases. The decrease of the dc-conductivity in the initial stage of cure is related to the time for gelation or vitrification. The contribution of the dipole relaxations to the dielectric permittivity reflects an increase of the relaxation times with curing time for both phases. The time-dependent changes in the complex dielectric permittivity are described by a simple two-phase model based on two Havriliak-Negami functions combined with Vogel-Fulcher equations for the description of the curing-time dependence of the relaxation times. The increase of the relaxation times in the phases during isothermal curing is incorporated by time-dependent Vogel temperatures. The latter are related to the time evolution of the glass-transition temperatures in the two phases measured independently by calorimetry. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2461-2470, 1998
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2499-2511 
    ISSN: 0887-6266
    Keywords: heat capacity ; poly(trimethylene terephthalate) ; entropy ; enthalpy ; free enthalpy ; heats of transition ; glass transition ; melting ; crystallinity ; rigid-amorphous fraction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat capacity of poly(trimethylene terephthalate) (PTT) has been measured using adiabatic calorimetry, standard differential scanning calorimetry (DSC), and temperature-modulated differential scanning calorimetry (TMDSC). The heat capacities of the solid and liquid states of semicrystalline PTT are reported from 5 to 570 K. The semicrystalline PTT has a glass transition temperature of 331 K. Between 340 and 480 K, PTT can show exothermic ordering depending on the prior degree of crystallization. The melting endotherm of semicrystalline samples occurs between 480 and 505 K, with a typical onset temperature of 489 K (216°C). The heat of fusion of the semicrystalline samples is about 15 kJ mol-1. For 100% crystalline PTT the heat of fusion is estimated to be 30 ± 2 kJ mol-1. The heat capacity of solid PTT is linked to an approximate group vibrational spectrum and the Tarasov equation is used to estimate the heat capacity contribution due to skeletal vibrations (θ1 = 550.5 K and θ2 = θ3 = 51 K, Nskeletal = 19). The calculated and experimental heat capacities agree to better than ±3% between 5 and 300 K. The experimental heat capacities of liquid PTT can be expressed by: \documentclass{article}\pagestyle{empty}\begin{document}$ C^L_p(exp) $\end{document} = 211.6 + 0.434 T J K-1 mol-1 and compare to ±0.5% with estimates from the ATHAS data bank using contributions of other polymers with the same constituent groups. The glass transition temperature of the completely amorphous polymer is estimated to be 310-315 K with a ΔCp of about 94 J K-1 mol-1. Knowing Cp of the solid, liquid, and the transition parameters, the thermodynamic functions enthalpy, entropy, and Gibbs function were obtained. With these data one can compute for semicrystalline samples crystallinity changes with temperature, mobile amorphous fractions, and resolve the question of rigid-amorphous fractions.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2499-2511, 1998
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 755-761 
    ISSN: 0887-6266
    Keywords: positron annihilation lifetime spectroscopy ; free volume ; transition temperatures ; poly(silylenemethylene)s ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amorphous and crystalline poly(silylenemethylene)s with the repeating PhRSiCH2 (R : Me or Ph) units were characterized by positron annihilation lifetime spectroscopy (PALS) to gain insights into the molecular motions of these polymers. The temperature dependence of the ortho-positronium lifetime (τ3) and intensity (I3) was examined from 50 to 470 K for each sample. The glass transition temperature of each polymer was easily distinguished by a change in the slope of τ3 spectrum. Both polymers exhibited a steep drop of I3 at 130-140 K being probably assignable to the transition arising from the motions of phenyl groups, which was almost undetectable by means of differential scanning calorimetry or dynamic mechanical analysis. Several other transitions of these polymers detected by PALS are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 755-761, 1998
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 797-803 
    ISSN: 0887-6266
    Keywords: polynorbornene ; gas separation ; membrane ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of gas transport properties of novel polynorbornenes with increasing length of an aliphatic pendant group R (CH3—, CH3(CH2)3—, CH3(CH2)5—, CH3(CH2)9—) has been performed. These polymers were synthesized using novel organometallic complex catalysts via an addition polymerization route. This reaction route maintained the bridged norbornene ring structure in the final polymer backbone. Gas permeability and glass transition temperature were found to be higher than those for polynorbornenes prepared by ring-opening metathesis and reported in the literature. It was shown that for noncondensable gases such as H2 and He the selectivity over N2 decreased when the length of the pendant group increased, but remained relatively stable for the more condensable gases (O2 and CO2). The permeability coefficient is correlated well to the inverse of the fractional free volume of the polymers. The more condensable gases showed a deviation from this correlation for the longest pendant group, probably due to an increase of the solubility effect. This polymer series demonstrated a simultaneous increase in permeability and selectivity, uncommon for polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 797-803, 1998
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 861-871 
    ISSN: 0887-6266
    Keywords: glass transition ; polymer blends ; free volume ; positron annihilation ; composition dependence of Tg ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-Vinyl Polybutadiene (HVBD)/cis-Polyisoprene (CPI) blends were characterized by Differential Scanning Calorimetry (DSC) and Positron Annihilation Lifetime Spectroscopy (PALS). A single DSC glass transition temperature Tg is observed, whose composition dependence strongly deviates from additivity, and shows an apparent cusp when the weight fraction of HVBD ≈ 0.75. The free-volume hole size, Vh, and the scaled fractional free volume, hps/C, = I3Vh were determined by PALS from the orthopositronium (o-Ps) intensities, I3, and lifetimes, τ3, over a temperature range encompassing Tg and the temperature at which “positronium bubble” formation occurs. In the glass, Vh and hps/C are smaller for CPI than for HVBD, but the thermal expansion coefficient for hole volume, αf, is larger in the melt for CPI than for HVBD; thus, an iso-hole volume temperature occurs in these blends at Tiso ≈ -34°C. Above and below Tiso, Vh and hps/C each show a negative departure from additivity. A quantitative interpretation of the cusp in the composition dependence of Tg can be obtained, via a modified analysis of Kovacs, using free-volume quantities from PALS, with the ratio of scaling constants CCPI/CHVBD as an adjustable parameter. At high temperatures, the positron bubble size is smaller in CPI than in HVBD. This agrees with the observation that the thermal expansivity of hole volume, and, hence the internal pressure are larger in the equilibrium melt of CPI. The effect of e+-irradiation on the o-Ps intensity was investigated. I3 decreases more rapidly in the melt as T → Tg, and then more slowly in the glass, suggesting that the effect is due to trapping of radical or ionic species which inhibit o-Ps formation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 861-871, 1998
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 463-471 
    ISSN: 0887-6266
    Keywords: hydrogel ; free volume ; positron annihilation ; water ; density ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A copolymer of 2-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 463-471, 1998
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1465-1481 
    ISSN: 0887-6266
    Keywords: poly(phenylene) ; dielectric ; dynamic mechanical ; relaxation ; free volume ; positron annihilation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free volume and related mobility properties of substituted poly(p-phenylene) polymers are examined. The techniques used range from positron annihilation, dielectric relaxation, and dynamic mechanical spectroscopy to thermally stimulated currents. Fractional free volume is determined for the samples with different substituted side groups and related to the glass transition temperature. Bulkier groups lead to a greater fractional free volume and lower glass transition temperatures. Comparison of molecular relaxation times using the different characterization techniques demonstrates that there is strong coupling between motion of the main chain and the side groups, on which the dipoles reside. Intermolecular coupling between the main chains at the primary relaxation is shown in this work to be related to the nature of the side chains and resultant free volume, as are the temperature locations of local, secondary relaxations. A qualitative model describing the effect of regiochemistry on the motions and packing of these materials is also proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1465-1481, 1998
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  • 10
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1839-1845 
    ISSN: 0887-6266
    Keywords: positron annihilation ; polymers ; free volume ; plasticization of polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron lifetime measurements in pure polyvinyl chloride (PVC) and in the plasticized PVC have been performed. Tricresyl phosphate was used as a plasticizer. Samples of the PVC were prepared with eight different plasticizer concentrations (from 0 to 35% of the plasticizer in the PVC). All of the measurements were performed in air at room temperature. A conventional fast-slow coincidence lifetime spectrometer was used for the measurements. Mean free volumes radii and fractional free volumes were calculated from the lifetime data. It has been found that the mean free volume radius is in the investigated region of the plasticizer concentrations, a linear function of the concentration of the tricresyl phosphate in the PVC. It seems that a polynomial fit can be used to describe the fractional free volume vs. the plasticizer concentration in the PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1839-1845, 1998
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  • 11
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1371-1382 
    ISSN: 0887-6266
    Keywords: epoxy resins ; thermosets ; glass transition ; yield behavior ; fracture toughness ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of crosslink functionality (fc), molecular weight between crosslinks (Mc), and chain stiffness display on the thermal and mechanical behavior of epoxy networks are determined. Both fc and Mc are controlled by blending different functionality amines with a difunctional epoxy resin. Chain stiffness is controlled by changing the chemical structure of the various amines. In agreement with rubber elasticity theory, the rubbery moduli are dependent on fc and Mc, but independent of chain stiffness. The glassy moduli and secondary relaxations of these networks are relatively independent of fc, Mc, and chain stiffness. However, the glass transition temperatures (Tg) of these networks are dependent on all three structural variables. This trend is consistent with free volume theory and entropic theories of Tg. fc, Mc, and chain stiffness control the yield strength of these networks in a manner similar to that of Tg and is the result that both properties involve flow or relaxation processes. Fracture toughness, as measured by the critical stress intensity factor (KIc), revealed that fc and Mc are both critical parameters. The fracture behavior is the result of the fracture toughness being controlled by the ability of the network to yield in front of the crack tip. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1371-1382, 1998
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  • 12
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1513-1528 
    ISSN: 0887-6266
    Keywords: free volume ; thermal expansion ; positron lifetime measurements ; semicrystalline polymers ; polyethylene ; polytetrafluoroethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron lifetime measurements, performed in the temperature range 80-300 K, are reported for polyethylene (PE) and polytetrafluoroethylene (PTFE). The lifetime spectra have been analyzed using the data processing routines LIFSPECFIT and MELT. Two long-lived components appear, which are attributed to pick-off annihilation of ortho-positronium in crystalline regions and at holes in the amorphous phase. The ortho-positronium lifetimes, τ3 and τ4, are used to estimate the crystalline packing density and the size of local free volumes in the crystalline and amorphous phases. The interstitial free volume in the crystals exhibits a weak linear increase with the temperature which is attributed to thermal expansion of the crystal unit cell. In the amorphous phase, the hole volume varies between 0.053 and 0.188 nm3 (PE) and between 0.152 and 0.372 nm3 (PTFE). Its temperature variation may be fitted by two straight lines, the intersection of which is used to estimate a glass transition temperature of Tg = 195 K for both PE and PTFE. The slopes of the free volume in the glassy and crystalline phases with the temperature correlate well with each other. The coefficients of thermal expansion of the hole volume are compared with the macroscopic volume change below and above the glass transition. From this comparison a fractional hole volume at Tg of 4.5 (PE) and 5.7% (PTFE) and a number of 0.73 (PE) and 0.36 (PTFE) × 1027 holes/m3 is estimated. Finally, it is found that the intensity of o-Ps annihilation in crystals shows a different temperature dependence to that in the amorphous phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1513-1528, 1998
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  • 13
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1739-1746 
    ISSN: 0887-6266
    Keywords: block copolymers ; molecular diffusion ; Forced Rayleigh scattering ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to transport in a high molecular weight SI diblock copolymer (Mn = 13,600) that has been solvated sufficiently in toluene to be microstructurally disordered. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1739-1746, 1998
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  • 14
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 913-918 
    ISSN: 0887-6266
    Keywords: glass transition ; thermally stimulated currents (TSC) ; relaxation ; PVC ; dielectric ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated current-thermal sampling (TSC-TS) technique was used to study the broadened glass transition in conventional “atactic” poly(vinyl chloride), PVC. The activated parameters obtained from the TSC-TS data, mainly the apparent activation energy (Ea), characterize the breadth of glass transitions in a very sensitive way. These results are compared with those values of Ea obtained from the literature, using a recently proposed method of analyzing a.c. dielectric constants and their derivatives, over the temperature range of -100-130°C. Both techniques detect weak cooperative glass transition-like relaxations well below the main glass transition of ca. 80°C. As is the case with “atactic” PMMA, the data suggest that compositional heterogeneity related to a small fraction of predominantly isotactic sequences contribute to the broad glass transition extending ca. 60°C below the main glass transition in atactic PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 913-918, 1998
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  • 15
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1037-1050 
    ISSN: 0887-6266
    Keywords: polymer glasses ; glass transition ; diluents ; antiplasticization ; mixtures ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model to describe the specific volume of glassy mixtures of a polymer and a low molecular weight diluent or additive is presented. The model is based on understandable physical assumptions and relies on parameters that can be determined experimentally or estimated from methods available in the literature. The predictions of the model show good agreement with the experimental data for mixtures of four polymers with diluents that in the pure state are liquid, glassy, or crystalline. The observed negative departure from volume additivity, as defined by simple additivity of the specific volume of the pure glassy polymer and the pure amorphous diluent, is the result of the relaxation of the excess volume of the glassy mixture relative to the equilibrium state caused by mixing two components with different glass transition temperatures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1037-1050, 1998
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  • 16
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2111-2128 
    ISSN: 0887-6266
    Keywords: orientation ; physical aging ; free volume ; glass-transition ; dilatometry atactic-polystyrene ; bisphenol A polycarbonate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has recently been demonstrated that hot-drawn samples of bisphenol A polycarbonate (PC) have a 50% higher volume relaxation rate than their isotropic counterpart even though the oriented samples have a lower initial free volume (i.e., higher density).1 In an attempt to better understand this paradox, samples of unaged, hot-drawn PC were characterized thermodynamically and kinetically as a function of orientation. Heat capacity, hole energy, and Tg data indicate that the chain mobility is actually decreasing slightly with orientation, possibly due to the hindered motion brought about by tighter packing, stronger intermolecular bonding, and reduced free volume. Nonetheless, this decrease in localized mobility is in contradiction to the enhanced volume relaxation rates observed for the oriented samples. In contrast, dynamic mechanical data indicate an increase in the relaxation strength of the β-transition (-100°C at 1 Hz) upon stretching for both the stretch and transverse directions. This implies that more segments are actively participating in the relaxation process for the oriented samples even though their individual localized mobility might be slightly lower. The net result is an increase in “effective” mobility for the oriented samples. It is conjectured that the enhanced relaxation strength of the oriented samples is a result of the stretching process somehow activating more of the chains into a higher energy state, and may be related to the physical aging concept of stress-induced rejuvenation/acceleration. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2111-2128, 1998
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  • 17
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2165-2175 
    ISSN: 0887-6266
    Keywords: temperature-modulated differential scanning calorimetry ; DSC ; heat capacity ; glass transition ; thermal relaxation ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition can be measured at different experimental conditions. Using spectroscopic methods at relative high frequency the α-relaxation is measured in the thermodynamic equilibrium. In the caloric case we call this phenomenon thermal relaxation transition (TRT). With a conventional differential scanning calorimeter (DSC) the transition of the equilibrium (the melt) into a nonequilibrium (the glassy state) is measured. This effect is called thermal glass transition (TGT). In contrast to the TGT, the TRT can be described using the linear response approach. The temperature-modulated differential scanning calorimetry (TMDSC) technique superimposes a periodical temperature perturbation upon the constant scanning rate of conventional DSC. This technique combines a spectroscopic method with a linear temperature scan. Both the TGT and the TRT are measured simultaneous. Because the frequencies are relatively low in a TMDSC experiment, the temperature ranges of both transitions overlap. In this case, the experimental results show an influence of the TGT on the TRT. The reason of that is the deviation from the nonequilibrium. In this case, the fictive temperature is different from the external temperature. This effect can be described by means of a Tool-Narayanaswamy-Moynihan model for the TGT. Based on this model, a description of the complex heat capacity close to the thermal glass transition is shown. The influence of the beginning freezing-in process on the thermal relaxation is characterized by the fictive temperature. Using the presented description, a quantitative calculation of the nonlinear effects in the thermal relaxation is possible. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2165-2175, 1998
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  • 18
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3035-3048 
    ISSN: 0887-6266
    Keywords: epoxy ; absorption ; water ; positron annihilation lifetime spectroscopy ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epoxy resins absorb significant quantities of moisture, typically 1 to 7% by weight for various formulations, which can greatly compromise their physical properties. It is known that polarity of the epoxy is a significant factor in determining the ultimate moisture uptake. However, the contribution from molecular topology still remains vague. In this work, the effects of molecular topology are elucidated by synthesizing novel epoxies where the polarity is maintained constant but the topology is systematically altered. The molecular topology is quantified in part via Positron Annihilation Lifetime Spectroscopy (PALS) in terms of the nanometer-sized voids, or nanovoids, that are also commensurate with typical interchain distances. The nanovoids are separated into their absolute zero and thermally fluctuating fractions by performing PALS measurements over a wide range of temperatures. A strong correlation is observed between the absolute zero hole volume fraction and the ultimate moisture uptake. Although the correlation is clear, the absolute zero hole volume fraction alone is not sufficient to predict the ultimate moisture uptake, and network polarity must also be considered. It is surmised that the role of the nanovoids is to open the epoxy matrix and alleviate steric hindrances that may prevent a water molecule from associating with a polar group. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3035-3048, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3049-3056 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free volume ; polysulfone ; CO2 gas exposure ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron annihilation lifetime (PAL) spectroscopy has been employed to study subnanometer hole properties in polysulfone (PSF). In this study, hole properties of size, fraction, and distribution of PSF exposed to CO2 are reported. In the PSF/CO2 system, the hole size and fraction significantly increase and the free-volume distribution broadens as a function of CO2 pressure in the range of 0-1000 psi. Hysteresis in hole properties is observed during CO2 sorption/desorption cycle. The high sensitivity of PAL results due to CO2 exposure in PSF is explained in terms of the microstructural changes in the polymer matrix, i.e., filling penetrant and plasticization, gas hydrostatic pressure effect, and creation of free volumes and holes. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3049-3056, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1141-1151 
    ISSN: 0887-6266
    Keywords: polymer gel ; poly(N-isopropylacrylamide) ; PNIPA ; volume phase transition ; hydrogen bond ; hydrophobic interaction ; free volume ; positronium ; positron annihilation ; methanol-water mixed solvent ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The macroscopic volume shrinkage and swelling of poly(N-isopropylacryl-amide) (PNIPA) gel induced by the compositional change in the methanol-water mixed solvent is correlated to the change in the nanoscopic free volume size and numerical concentration formed in the PNIPA gels. The free volume size and numerical concentration are estimated from the longest component appearing in the positron annihilation lifetime curves. The apparent free volume fraction calculated by the free volume size and numerical concentration, and dispersion of the free volume deduced by the size distribution are utilized to analyze the origin and location of the free volumes. The free volume parameters obtained by analysis of the positron annihilation data show various nanoscopic phases occuring within the PNIPA gels during the volume change, implying the variation of the strength of the interactions among the solvent molecules and the polymer chains of the PNIPA. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1141-1151, 1998
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1-31 
    ISSN: 0887-6266
    Keywords: Rouse model ; reptation ; glass transition ; Monte Carlo method ; bond fluctuation model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A brief review is given of applications of Monte Carlo simulations to study the dynamical properties of coarse-grained models of polymer melts, emphasizing the crossover from the Rouse model toward reptation, and the glass transition. The extent to which Monte Carlo algorithms can mimic the actual chain dynamics is critically examined, and the need for the use of coarse-grained rather than fully atomistic models for such simulations is explained. It is shown that various lattice and continuum models yield qualitatively similar results, and the behavior agrees with the findings of corresponding molecular dynamics simulations and experiments, where available. It is argued that these simulations significantly enhance our understanding of the theoretical concepts on the dynamics of dense macromolecular systems. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 59-67 
    ISSN: 0887-6266
    Keywords: nanocomposites ; glass transition ; confined chains ; intercalation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of poly(ethylene oxide) (PEO), intercalated in montmorillonite, a naturally occurring mica-type silicate, was studied by differential scanning calorimetry (DSC) and thermally stimulated dielectric depolarization (or thermally stimulated current, TSC). The materials were synthesized by melt or solution-mediated intercalation. In both intercalates, the PEO chains were confined to ca. 0.8-nm galleries between the silicate layers. The solution intercalate contained a fraction of unintercalated PEO chains which exhibited a weak and depressed PEO melting endotherm in DSC. In contrast, the melt intercalate was “starved” such that almost all the PEO chains were effectively intercalated. For these melt intercalates, no thermal events were detected by DSC. TSC thermal sampling technique was used to examine the glass transition regions and to estimate the extent of cooperativity of chain motions. The motions of the intercalated PEO chains are inherently noncooperative relative to the cooperative Tg motions in the amorphous portion of the bulk polymer. This is presumably due to the strong confining effect of the silicate layers on the relaxations of the intercalated polymer. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1601-1609 
    ISSN: 0887-6266
    Keywords: positron annihilation ; polyethylene ; polypropylene ; polystyrene ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition and relaxation processes of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were studied by the positron annihilation technique. From measurements of lifetime spectra of positrons as a function of temperature, the lifetime of ortho-positronium, τ3, and its intensity, I3, were found to increase above 260 K for PP. This fact was attributed to a cooperative motion of large segments of molecules above the glass transition temperature, Tg. For PE, above Tg (140 K), the value of τ3 increased, but the temperature coefficient of I3 was negative below 230 K. From this fact, for PE, the molecular motions that cause the glass transition were associated with a rearrangement of molecules by local motions such as kink motions. The discrepancy between the results for PE and PP was attributed to the presence of methyl groups in PP and the resultant suppression of the local motions. For PS (Tg = 340 K), the molecular motions were found to start above 260 K, but those were suppressed by an interphenyl correlation. Detailed annihilation characteristics of positrons in polymers were also discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1601-1609, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1737-1746 
    ISSN: 0887-6266
    Keywords: free volume ; dual mode ; diffusion ; glassy polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of a new model for the diffusion of gas molecules in glassy polymers is presented which utilizes concepts from free volume theory and relies on a dual-mode interpretation of sorptive dilation in glassy polymers. Three assumptions are made in the development of the model. First, the free volume available for molecular transport processes is taken as constant below the glass transition temperature. Second, two populations of gas molecules are assumed to exist - one which contributes to the maintenance of an iso-free volume state upon sorptive dilation and one which does not contribute owing to sorption into regions of unrelaxed volume. Third, the former population is assumed to be mobile while the latter is not. The resulting model predicts, at constant temperature, a diffusion coefficient that is independent of solute volume fraction. This is in contrast to the widely used dual-mode sorption model with partial immobilization for gas transport in glassy polymers which leads to a diffusion coefficient that is dependent on solute mole fraction through the molar gas concentration. The new model is used to interpret gas transport data from permeation experiments for carbon dioxide, methane, and ethylene in three polycarbonates. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1737-1746, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2121-2132 
    ISSN: 0887-6266
    Keywords: POM ; poly(oxy methylene) ; Delrin® ; dielectric ; TSC ; semicrystalline amorphous ; thermally stimulated currents ; glass transition ; PTFE ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(OxyMethylene) (POM) and its miscible blends were studied by multifrequency A.C. dielectric and thermally stimulated currents (TSC). The blends contained small amounts of either poly(vinyl phenol), which is a high glass transition (Tg) diluent, or a styrene-co-hydroxy styrene oligomeric low Tg diluent. The variation of the 10°C “β” transition with blend composition proves that it is the glass transition, and that the -70°C “γ” transition is a local motion. Dielectrically the β transition is very weak in pure POM even in fast-quenched samples. The TSC thermal sampling method also detected two cooperative transitions, γ and β, in POM and its blends, and was used to directly resolve the γ transition into low and high activation energy components. If one considers the contribution of exclusion of the diluents from the crystal lamellae, it is shown that the blends behave like typical amorphous blends as a function of concentration. The effect of crystals on amorphous motions is examined in light of comparison with van Krevelen's37 predictions of an “amorphous” Tg, and the transitions in POM are contrasted with those for other semicrystalline polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2121-2132, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1561-1573 
    ISSN: 0887-6266
    Keywords: glass transition ; isobaric ; isochoric ; polymer ; poly(carbonate) ; PVT behavior ; free volume theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pressure-volume-temperature (PVT) studies were performed on a glass-forming polymer, poly(carbonate) (PC), under both isobaric and isochoric (constant volume) conditions. An isochoric glass transition was observed and the formation points were found to be consistent with those obtained isobarically. Although the isobaric and isochoric responses were, as expected, the same in the rubbery state, the glassy state values were found to be different and dependent upon the glass formation history. The isobaric data exhibited larger changes in going from the rubber to the glass, hence a “stronger” glass transition, than did the isochoric data. Inserting the experimental values for the thermal expansion coefficient α and isothermal compressibility β, into appropriate thermodynamic relations, measures of the strength of each transition are defined. Strength estimates based on literature values of α and β are compared to the experimental measures of the isochoric and isobaric transitions. In addition, both the isobaric and isochoric PVT results were analyzed in terms of the Fox and Flory free volume theory which assumes that the glass transition is an iso-free volume state. While the isobaric results were consistent with the Fox and Flory theory, the isochoric results were not consistent with the idea of an iso-free volume glass transition. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1561-1573, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1855-1868 
    ISSN: 0887-6266
    Keywords: gas permeability ; permselectivity ; activation energies ; free volume ; polyimides ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas transport of helium, hydrogen, carbon dioxide, oxygen, argon, nitrogen, and methane in three soluble poly(phenylene sulfone imide)s based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride (6FDA) has been investigated. The effects of increasing length of well-defined oligo(phenylene sulfone) units on the gas permeabilities and diffusivities were determined and correlated with chain packing of the polymers. Activation energies of diffusion and permeation were calculated from temperature-dependent time-lag measurements. The influences of the central group in the diamine moiety of 6FDA-based polyimides on physical and gas transport properties are discussed. The incorporation of a long oligo(phenylene sulfone) segment in the polymer backbone decreases gas permeability and permselectivity simultaneously. The decreases in permeability coefficients can be mainly related to decreases in diffusion coefficients. Changing the central group of diamine moiety from —S— to —SO2— leads to a 45-50% decrease in CO2 and O2 permeabilities without appreciable increase in the selectivities. This is considered to be due to the formation of charge transfer complexes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1855-1868, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 153-163 
    ISSN: 0887-6266
    Keywords: epoxy resin ; thermoplastic ; dynamical mechanical spectroscopy ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical spectroscopy has been used to investigate the cure of a thermoplastically modified trifunctional epoxy resin. The complex dissolution, curing behavior, and variations in the glass transition of the thermoplastic (PSF) phase were described, as was the Tg behavior of the epoxy phase. Prereaction of the PSF material with the epoxy resin was found to greatly increase the solubility of the PSF in the epoxy phase with little effect on the concentration of the epoxy monomer dissolving in the PSF phase. The curing behavior of the epoxy component in the thermoplastic phase was also investigated, in addition to changes in the mobility of the network at both gelation and vitrification. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 771-776 
    ISSN: 0887-6266
    Keywords: Nafion ; positron annihilation ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result on positron annihilation studies in acid- and cation-neutralized (Li+, Na+, K+, Rb+, Cs+, UO22+, Ni2+) Nafion membranes using positron lifetime and Doppler-broadened annihilation radiation (DBAR) measurements. The free-volume structure is characterized using a simple quantum mechanical model of positronium (Ps) in a spherical well. Our studies indicate that formation and expansion of clusters is always associated with a change in free-volume structure resulting in smaller free-volume holes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 771-776, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2483-2493 
    ISSN: 0887-6266
    Keywords: polyvynilidenefluoride ; glass transition ; thermally stimulated depolarization current ; dielectric loss ; relaxation times distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The αa-mode (associated to the dynamic glass transition) in PVDF-α has been studied by Thermally Stimulated Depolarization Currents (TSDC) and Dielectric Spectroscopy (DS) techniques. The distribution of relaxation parameters, reorientation energies, characteristic temperature, and preexponential factors of the Vogel-Tammann-Fulcher relaxation times have been precisely determined by using the Simulated Annealing Direct Signal Analysis applied to a partially discharged TSDC αa peak. This distribution has been used to predict the variation of the dielectric loss, ε″(ω, T), in the temperature and frequency range where the DS measurements were made on the same material. The simulated ε′(T, ω) for various ω, are compared to the experimental values. The width of the peak is always too low, due to the restricted distribution used for the generation of the curves. A relaxation map including the TSDC results is used to determine the relaxation time variation. In the limited frequency range where the AC DS experiments are performed (102 ≤ f ≤ 105 Hz) a master curve is drawn and the exponents of the frequency dependence are found at low and high frequency; also, a fitting to the Havriliak-Negami distribution is successfully performed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2483-2493, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 807-815 
    ISSN: 0887-6266
    Keywords: moisture effect ; glass transition ; low temperature relaxations ; semiaromatic amorphous polyamides ; hydrogen bonding ; molecular analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of moisture absorption on the primary (glass) transition (Ta or Tg) and the low temperature relaxations of semiaromatic amorphous polyamides synthesized by isomeric aliphatic diamine and metha or para oriented phthalicdiacids has been investigated by means of differential scanning calorimeter (DSC) and dynamic mechanical thermal analyser (DMTA). The glass transition of semiaromatic polyamides was lowered due to the water absorption, and the β and the γ relaxations were as well. From the observed Tg and the difference in the heat capacity, the calculated Tg depression per 1 wt % water content was 12.3 K and the result was in good agreement with the experimental data. The depression of the glass transition may be expressed by the same manner as the plasticization of nylon 6 by water. The depressed β relaxation observed in the specimen containing a few percent of moisture was splitted into two transitions due to the reduction of water content, of which one was the elevation of the Tβ and another was the simultaneous appearance of the Tγ, and then the single Tγ solely was observed for the completely dried specimen. The Tγ seemed to be merged into or not to be observed by the large and broad Tβ transition when the sample was governed by a few percent of water, then it was emerged from the Tβ due to water desorption. Thus, the Tβ is believed to arise from the intermolecular hydrogen bonding between water molecules or between water and amide groups in wet polyamides. In addition, the γ relaxation originated from the peptide groups is attributable to the inter- and intramolecular hydrogen bonding between amide groups. © 1997 John Wiley & Sons, Inc. J Polyn Sci B: Polym Phys 35: 807-815, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 523-534 
    ISSN: 0887-6266
    Keywords: polymer solutions ; supercritical fluids ; non-Newtonian viscosity ; free volume ; polydimethylsiloxane ; carbon dioxide ; capillary rheometer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosity curves were measured for polydimethyl siloxane (PDMS) melts swollen with dissolved carbon dioxide at 50 and 80°C for shear rates ranging from 40 to 2300 s-1, and for carbon dioxide contents ranging from 0 to 21 wt %. The measurements were performed with a capillary extrusion rheometer modified for sealed, high-pressure operation to prevent degassing of the melt during extrusion. The concentration-dependent viscosity curves for these systems are self-similar in shape, exhibiting low-shear rate Newtonian plateau regions followed by shear-thinning “power-law” regions. Considerable reduction of viscosity is observed as the carbon dioxide content is increased. Classical viscoelastic scaling methods, employing a composition-dependent shift factor to scale both viscosity and shear rate, were used to reduce the viscosity data to a master curve at each temperature. The dependence of the shift factors on polymer chain density and free volume were investigated by comparing the shift factors for PDMS-CO2 systems to those obtained by iso-free volume dilutions of high molecular weight PDMS. This comparison suggests that the free volume added to PDMS upon swelling with dissolved carbon dioxide is the predominant mechanism for viscosity reduction in those systems. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 523-534, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1107-1116 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; conformational energy ; free volume ; glass transition ; side chains ; physical ageing ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpy changes ΔH∞ between a poly(vinyl acetate) glass formed by rapid cooling and the corresponding fully relaxed glass have been estimated at four temperatures below the glass transition. The values obtained were different to those expected by extrapolating liquid behavior below the glass transition and were found to agree well with the predictions of a simple expression for the combined main chain conformational and free volume contributions to enthalpy. Conformational contributions from the side chain alone were also considered but were not required to obtain agreement with experiment. It can be concluded that the side chains remained mobile below the glass transition and do not contribute to the heat capacity discontinuity at Tg. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1107-1116, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2879-2888 
    ISSN: 0887-6266
    Keywords: nylon-6 ; dry and water saturated ; thermally stimulated depolarization current ; dielectric relaxation ; glass transition ; water sorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of water sorption on the dielectric relaxation processes of nylon-6 samples with water concentrations ranging from the dry to the water-saturated polymer has been studied by thermally stimulated depolarization currents experiments in a broad temperature range, from 77 to 365 K. The strengths of the low-temperature modes, γ- and β-peaks, are affected in opposite ways by the water concentration, h, as the first one shows a decrease in intensity and the second one grows as h increases. The precise determination of the relaxation parameters is made by the decomposition in elementary Debye processes and best fitting to the experimental profile of the complex peak. For h 〈 3%, the reorienting energies are almost independent of the water content, and the most significant intensity variations occur. The firmly bound water is held responsible for these effects. As for the higher temperature zone besides the α-peak, which is the dielectric manifestation of the glass transition, intermediate temperatures modes are observed at high h values and are originated by the loosely bound water, while the highest temperature peak is attributed to a Maxwell-Wagner interfacial polarization. The characteristic parameters of the α-mode are determined and related to the plasticization effect of water. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2879-2888, 1997
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    ISSN: 0959-8103
    Keywords: semi-interpenetrating polymer networks ; filler ; dynamic mechanical properties ; glass transition ; microphase separation ; Chemistry ; Polymer and Materials Science
    Source: Wiley 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 preparation of filled two-component semi-interpenetrating polymer networks (semi-IPNs) is described and the results of an investigation of their morphology by means of dynamic mechanical spectroscopy are considered. The influence of an active dispersed filler (γ-Fe2O3) on the semi-IPNs phase structure is studied. A comparison is made between filled and unfilled semi-IPNs consisting of compatible or incompatible polymers. In the case of a semi-IPN of compatible polymers, the introduction of γ-Fe2O3 was observed to cause phase separation. With a two-phase semi-IPN the introduction of the filler enhanced the phase separation. The presence of two distinct peaks (the dynamic glass transition temperatures) corresponding to those of the two initial homopolymers shows the semi-IPN to have a two-phase structure.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 401-417 
    ISSN: 0887-6266
    Keywords: polyurethane ; polyurethane acrylate ; glass transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear polyurethane, linear segmented polyurethane, polyurethane networks, and polyurethane acrylate networks of various composition were synthesized. The variation of Tg with the type of macrodiol, its length, and the chemical composition of the polymer were studied in relation with the percentage of soft segments, the molar mass between crosslinks, and the concentration of urethane bonds. In this work, the networks were considered as composed of chain segments of various composition between point-like crosslinks. The chemical heterogeneities of the networks were not taken into account. For polyurethanes, it was shown that Tg values are essentially controlled by the amount of urethane bonds. For polyurethane acrylates, the Tg values are dependent on the amount of urethane bonds but also on the presence of crosslinks whose number is varying with the excess of diisocyanate of the first step three times faster for PUA compared with PU. No clear relation was observed between Tg and the molar mass between point-like crosslinks. Another approach considering the network heterogeneities is indispensable and will be used in a following work. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 641-648 
    ISSN: 0887-6266
    Keywords: polyethylene ; glass transition ; TSDC ; γ transition ; β transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New thermally stimulated depolarization currents (TSDC) results on LLD polyethylene functionalized with diethylmaleate polar groups are precisely computer fitted with the direct signal analysis technique. It is shown that the TSDC spectrum consists, with increasing temperatures, of a sub-γ peak, a sharp γ peak, and a β and an α relaxation. The first peak is analyzed in terms of Arrhenius relaxation times, whereas the γ and β transitions could only be fitted by using Vogel-Fulcher temperature dependence for the relaxation times. The best value for To obtained from both fittings is 69.7 K. This is a quantitative proof for the identification of the γ transition as one of the dielectric manifestations of the glass-rubber transition for polyethylenes, Tg = 136.5 K, which has been discussed extensively in the literature. The β relaxation, Tgβ = 237 K, has also the expected characteristic of a glass transition; the existence of two Tgs in polyethylene could explain our results. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 341-348 
    ISSN: 0887-6266
    Keywords: ultrasonic measurement ; polystyrene ; glass transition ; relaxation ; Havriliak-Negami model ; Kauzmann temperature ; fragile glass ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report measurements of the temperature and pressure dependence of ultrasonic modulus and specific volume in polystyrene between 50 and 280°C and applied pressures up to 775 bar. The volumetric glass transition temperature is found to vary linearly with pressure. Furthermore, it coincides with the temperature at which the velocity of sound and the attenuation in the material show pronounced change from solid-like to liquid-like behavior. The storage and loss moduli are analyzed within the Havriliak-Negami model and very good agreement is found over the entire temperature and pressure ranges. Using the Vogel-Tammann-Fulcher equation for the relaxation time, the Kauzmann temperature Tk and the fragility parameter D of polystyrene were determined from fits to the data. Tk is also a linear function of pressure, but D is constant over the whole pressure range. The value of D allows us to classify polystyrene among the fragile-glass formers. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1613-1620 
    ISSN: 0887-6266
    Keywords: cellulose ester ; cellulose esterification ; cellulose acylation ; thermal analysis ; melting point ; glass transition ; side-chain crystallinity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cellulose esters with linear aliphatic acyl substituents ranging in size from C12 (lauric acid) to C20 (eicosanoic acid) were prepared in homogeneous solution (DMAc/LiCl) using a novel synthetic method based on the use of a mixed p-toluenesulfonic/carboxylic acid anhydride. The resulting waxy cellulose esters had a high degree of substitution (DS), between 2.8 and 2.9, and showed little degradation. Thermal analysis of these cellulose derivatives by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) revealed a series of transitions that represented motion by both ester substituents and cellulosic main chain. Broad crystallization and melting transitions attributed to side-chain crystallinity were observed in the range between -19 and +55°C; these side-chain Tm and Tc transition temperatures increased by 10°C per carbon atom of the ester substituent. The Tg of these derivatives increased linearly with increasing substituent size from 94°C for C12 (cellulose laurate) to 134°C for C20 (cellulose eicosanoate). Evidence of “main-chain” crystallization was not observed for these samples, except in the case of peracetylated C12 and C14 esters, which had Tm values of 96°C and 107°C, respectively. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2863-2879 
    ISSN: 0887-6266
    Keywords: semicrystalline polymers ; polycarbonate ; TSDC ; rigid amorphous phase ; glass transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermally Stimulated Depolarization Current technique, Differential Scanning Calorimetry, and Dynamic Mechanical Analysis have been applied to amorphous and semicrystalline bisphenol-A polycarbonate with crystallinity degrees up to 21.8%, in a temperature interval covering the α and β relaxations. The secondary β transition is found to be the sum of three components whose variations in aged and annealed specimens have shown the cooperative character of the β1 and β2 modes, contrary to the localized nature of the β3 component. A Tg decrease was observed by both TSDC and DSC as a function of Xc and has been related to the possible confinement of the mobile amorphous phase in regions whose sizes are smaller than the correlation lengths of the cooperative movements that characterize the motions occurring at Tg. The α relaxation intensity variations with crystallinity show the existence of an abundant rigid amorphous phase in the semicrystalline material. The relaxation parameters deduced from the Direct Signal Analysis of the α relaxation for the mobile amorphous phase do not show significant deviations from those found for the amorphous material. The existence of the rigid amorphous phase has been associated to the ductile-to-brittle transition experienced by the material at low crystallinity levels. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2941-2952 
    ISSN: 0887-6266
    Keywords: temperature-modulated calorimetry (TMC) ; temperature-modulated differential scanning calorimetry (TMDSC) ; heat capacity ; glass transition ; heat flow calorimeter ; irreversible thermodynamics ; activation energy ; poly(ethylene terephthalate) ; hysteresis ; enthalpy relaxation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Temperature-modulated differential scanning calorimetry is used to evaluate the kinetics of the glass transition from measurement of the first harmonic of the apparent, reversing heat capacity. The data are taken from quasi-isothermal experiments with negligible instrument lag, extrapolated to zero modulation amplitude. Equations based on irreversible thermodynamics that can be understood in terms of the hole theory of liquids are applied to measurements on amorphous, semicrystalline, and biaxially drawn poly(ethylene terephthalate)s (PET). The activation energy of amorphous PET decreases from 328 to 153 kJ/mol on crystallization and to 111 kJ/mol on orientation, and is correlated with an increase in the preexponential factor. After annealing of the crystallized samples below the glass transition temperature, the activation energy of the semicrystalline PET can recover beyond the level of amorphous PET, to 387 kJ/mol. The earlier observed decrease in enthalpy relaxation on crystallization is linked to this sharp decrease in activation energy. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1907-1915 
    ISSN: 0887-6266
    Keywords: Solubility ; EVOH ; glass transition ; organics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption isotherms of alcohols in EVOH copolymers were determined by inverse gas chromatography below and above the glass transition temperature. The sorbates studied were: methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, and t-butanol. From the sorption isotherms, Henry's law solubility coefficients (S) were evaluated and correlated to size, condensability, and (SINGLE BOND)OH position in the molecule as well as on temperature. Molecular dimension was an important factor, affecting the solubility via two contrary effects: molecular size and condensability. When comparing alcohols of the same size, primary alcohols were sorbed more than secondary alcohols and these more than tertiary alcohols at every temperature in the study. At low temperatures, the larger the size the greater the solubility, contrary to what was observed at high temperatures. Temperature effect on solubility was also tested applying Van't Hoff's equation. Since S behaved differently below and above Tg for every sorbate two values of the enthalpy of solution were obtained, positive above Tg and negative below Tg. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2145-2151 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free volume ; relaxation ; local motion of molecule ; micro-Brownian motion ; polyethylene ; polystyrene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation processes in polyethylene (PE) and polystyrene (PS) were studied by positron annihilation technique. For PE, above the glass transition temperature, Tg, the size of free volumes and its concentration were increased by the micro-Brownian motion of molecules. For PS, local motions of molecules in backbone chains were found to start above 260 K. However, these local motions were suppressed by an interphenyl correlation. For both PE and PS, below 250-260 K, the formation probability of positronium atoms increased with decreasing temperature. This fact was assigned to the freezing in of the local motions of molecules. For PS, an onset of the local motions of molecules was observed above 100 K. These motions were expected to be associated with liberation of phenyl groups. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 121-130 
    ISSN: 0887-6266
    Keywords: self-diffusion ; mutual diffusion ; activation energy ; free volume ; segmental motion ; inverse gas chromatography ; static gradient NMR ; 1,3,5-triisopropylbenzene ; polystyrene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Self-diffusion coefficients of 1,3,5-triisopropylbenzene (TIB) in binary solutions with polystyrene and ternary mixtures comprised of TIB, toluene, and polystyrene have been measured by static gradient nuclear magnetic resonance (SG-NMR) techniques. These data, as well as mutual-diffusion coefficient data measured by capillary column inverse gas chromatography (CCIGC), have been analyzed here with the Vrentas-Duda free-volume diffusion model. Although both binary and ternary diffusion coefficient data can be accurately correlated with the model, the results contradict those of an earlier investigation, which suggested that TIB diffuses as a single unit in polystyrene solutions. The new data suggest that either: 1) TIB diffuses by piece-wise displacements in polystyrene solutions, or 2) a diffusive activation energy ceiling value has been reached. The implications of both possibilities are discussed in the context of established free-volume principles. © 1996 John Wiley & Sons, Inc.
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  • 45
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2291-2305 
    ISSN: 0887-6266
    Keywords: glass transition ; polymer dynamics ; photon correlation spectroscopy ; dynamic heterogeneities ; longitudinal density fluctuations ; poly(n-hexyl methacylate) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Slowly relaxing longitudinal density fluctuations in an optically perfect sample of bulk poly(n-hexyl methacrylate) (PHMA) have been studied by photon correlation spectroscopy in the temperature range 10-36°C. The glass transition temperature for this sample was measured to be Tg = -3°C by differential scanning calorimetry. The optical purity of the sample was verified by Rayleigh-Brillouin spectroscopy and the Landau-Placzek ratio was observed to be 2.3 at 25°C. Light-scattering relaxation functions were obtained over the time range 10-6-1 s. The shape of the relaxation functions broadened as the temperature was lowered towards the glass transition. Quantitative analysis of the results was carried out using the Kohlrausch-Williams-Watts (KWW) function to obtain average relaxation times, 〈τ〉, and width parameters, β. The width parameter decreased from 0.43 to 0.21 over the temperature interval, as suggested by visual inspection. Average relaxation times shifted with temperature in a manner consistent with previous mechanical studies of the primary glass-rubber relaxation in PHMA. The relaxation functions were also analyzed in terms of a distribution of relaxation rates, G(Γ). The calculated distributions were unimodal at all temperatures. The average relaxation times obtained from G(Γ) were in agreement with the KWW analysis, and the shape of the distribution broadened as the sample was cooled. The rate at which G(Γ) displayed a maximum correlated well with the corresponding frequency of maximum dielectric loss for PHMA. The temperature dependence of these two quantities could be reproduced with an Arrhenius activation energy of 21 Kcal/mol. A consistent picture of the molecular dynamics of PHMA near the glass transition requires a strong secondary relaxation process with a different temperature dependence from the primary glass-rubber relaxation. The present results suggest that the behavior of PHMA is similar to the other poly(alkyl methacrylates). © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2635-2639 
    ISSN: 0887-6266
    Keywords: poly(methyl methacrylate) ; compressed gases ; glass transition ; plasticization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glass transition in the system poly(methyl methacrylate)/compressed gas was studied as a function of the gas pressure p using a high-pressure Tian-Calvet heat flow calorimeter. Measurements were made on PMMA-CH4-C2H4, and ;-CO2 at pressures to 200 atm. All three gases plasticize the polymer leading to depression of the glass transition temperature Tg. Trends in the Tg depression were the same as those reported for the solubility of these gases in PMMA; the higher the solubility the larger the depression in Tg. CO2 was found to be the most effective plasticizer producing a depression of about 40°C at a pressure of about 37 atm. In the low-pressure limit, the pressure coefficient of the glass transition temperature (dTg/dp) was found to be about -0.2°C atm-1 for PMMA-CH4, the same as that observed for polystyrene-CH4. For PMMA-C2H4, the pressure coefficient was -0.7°C atm-1, which is lower than the value of -0.9°C atm-1 observed for PS-C2H4. The pressure coefficient for PMMA-CO2 was found to be about -1.2°C atm-1, which is larger than the value of -0.9°C atm-1 observed for PS-CO2. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1189-1195 
    ISSN: 0887-6266
    Keywords: positron annihilation ; glass transition ; free volume ; polystyrene ; lifetime ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free volume characteristics in three samples of monodisperse polystyrene were investigated by positron annihilation technique over a temperature range from 300 to 380 K. The number-average molecular weight of the samples ranged from 5730 to 1,524,000. The observed lifetime spectra were resolved into three components, where the longest lifetime, τ3 was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by free volumes. The change of the temperature coefficient of τ3 was observed at around 350 K, at which the value of τ3 was a constant value of 2,3 ns for all specimens with different molecular weights. There was no discrete change of τ3 in intensity, which is corresponding to the number of free volumes. The size of free volume at glass transition was evaluated to be 0.l nm3. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2767-2770 
    ISSN: 0887-6266
    Keywords: positron annihilation ; positron lifetime ; free volume ; PTFE ; silica ; composites ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of PTFE/silica composites. The positron lifetimes (τn) and intensities (In) of PTFE and the composites (30-62% silica) were measured at room temperature as a function of specimen thickness. Four lifetime components were found in PTFE and the composites. The longer lifetime components, τ3 = 1.4 ns and τ4 = 4.4 - 4.1 ns, were interpreted to be due to the presence of two different sized free volume cavity distributions within the PTFE/silica composites. A strong silica concentration dependence was found in the bulk intensities (I3b and I4b). The I3b value increased from 13.0% in PTFE to 28.2% in the 62% composite, while the I4b value decreased from 17.5% in PTFE to 4.5% in the 62% composite. The smaller-void size, free volume fraction (τ3I3b) values increased linearly between 0 and 100% silica concentration, while the larger void size, free volume fraction (τ4I4b) values decreased nonlinearly with silica concentration. Since silica has a long lifetime component (τ3 = 1.6 ns), this behavior is ascribed to silica particles occupying the large free volume cavities (370 Å3) in the PTFE/silica composites. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2979-2985 
    ISSN: 0887-6266
    Keywords: anisotropy ; free volume ; oriented polymers ; positron annihilation ; correlation ; 2D-ACAR ; polycarbonate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two-dimensional angular correlation of annihilation radiation (2D-ACAR) experiments have been performed on an uniaxially oriented polymer, bisphenol-A polycarbonate. The two-dimensional hole structures of unoriented and oriented polymers, determined from the momentum distributions, are found to be spherical and ellipsoidal, respectively. The average hole radii are determined to be 2.9 Å in the unoriented sample and between 2.3 and 3.8 Å in the oriented sample. Applications of the 2D-ACAR method to image the three-dimensional hole structures of polymeric materials are discussed. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1659-1664 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free volume ; liquid-crystalline polymer ; nematic ; smectic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free volumes in thermotropic side-chain liquid-crystalline polymers were probed by positron annihilation technique. Lifetime spectra of positrons were measured in the temperature range between 130 and -60°C in cooling. For a nematic liquid-crystalline polymer (polyacrylate), the lifetime of ortho-positronium (τ3) was decreased with decreasing temperature above the glass transition temperature (Tg, 21°C) with larger temperature coefficient than that below Tg. The intensity of ortho-positronium (I3) was constant above Tg. These facts mean that the size of the free-volume holes decreased with the decreasing the temperature but the concentration was almost constant in nematic phase. For a smectic liquid-crystalline polymer (poly(p-methylstyrene) derivative), a discontinuous decrease in the value of τ3 and that of I3 were observed at 107°C, which was the transition temperature from smectic to crystalline phase. Such discontinuous changes were not observed for the polyacrylate specimen. This difference was considered to be attributed to the higher-ordered structure of the smectic phase. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2881-2892 
    ISSN: 0887-6266
    Keywords: poly(n-alkyl methacrylates) ; glass transition ; molecular cooperativity ; DSC ; heat capacity spectroscopy ; αβ splitting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The definition of molecular cooperativity is discussed. The characteristic length of the glass transition describes the size of this cooperativity. Differential scanning calorimetry (DSC) and heat capacity spectroscopy (HCS) results of a series of poly(n-alkyl methacrylates) (alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl) and a series of statistical copolymers poly(n-butylmethacrylate-stat-styrene) are discussed in terms of molecular cooperativity in the αβ splitting region, where a high-frequency dispersion zone a splits off into the main transition zone α and a Goldstein Johari process β at lower frequencies. The characteristic length tends to small values of order one monomer diameter in the splitting region for scenarios with an α relaxation onset. The statements about the size scale of cooperativity are conditional upon certain assumptions leading to the equation used for calculation of this size from HCS and DSC data. The step height of heat capacity (Δcp) and, with less certainty, the square root of the cooperativity volume or number (V1/2α or 1/2α) are proportional to the temperature distance from the cooperativity onset, T = Tons. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1903-1906 
    ISSN: 0887-6266
    Keywords: Positron annihilation ; polymers ; free volume ; plasticization of polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Positron lifetimes measurements in pure polyvinyl chloride (PVC) and in the plasticized PVC have been performed. Dioctyl phthalate has been used as a plasticizer. Samples have been prepared of the PVC with eight different plasticizer concentrations (from 0 to 35% of the plasticizer in the PVC). All of the measurements have been performed in air at room temperature. A conventional fast-slow coincidence lifetime spectrometer has been used for the measurements. Mean free volumes radii have been calculated from the lifetime data. It has been found that the mean free volumes radii are in the investigated region of plasticizer concentrations a linear function of the concentration of the dioctyl phthalate in the PVC. © 1996 John Wiley & Sons, Inc.
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  • 53
    ISSN: 0959-8103
    Keywords: miscible blends ; polyesters ; positron annihilation lifetime spectroscopy ; free volume ; Chemistry ; Polymer and Materials Science
    Source: Wiley 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 blend systems (miscible binary polyester blends) have been examined by positron annihilation lifetime spectroscopy (PALS). The ortho-Positronium pick off lifetime, τ3, is related to the mean free volume cavity size in these miscible blends. The measured free volume cavity size for the blends is compared to the size predicted from linear additivity of the homopolymers. A negative deviation from linear additivity is observed for τ3 in each of the blend systems, and this behaviour is interpreted as a contraction of the mean free volume cavity size due to the changes in molecular packing that occur on blending. The consequence of these free volume results for the mechanical properties of miscible polyester blends is discussed and tested for the polycarbonate/Kodar system. The glass transition data suggest weak specific interactions in the blends; however, the mechanical properties are significantly affected by blending.
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  • 54
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    Polymer Engineering and Science 35 (1995), S. 18-27 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Solid-catalyzed copolymerization reactions of ethylene and α-olefins can produce complex mixtures generally regarded as “polyethylenes” (including linear low-density polyethylene). The selective nature of those catalysts can lead to block-like character in segments of polymer molecules, and these segments are sufficiently dissimilar (from a thermodynamic viewpoint) to allow for the possibility of microphase separation in the melt. Such a molecular-level phase separation would substantially alter the melt rheology, the crystallization process, and hence the mechanical and optical properties of the resulting product. It would, in principle, be identical to those occurring in conventional well-defined block copolymers, allowing the thermodynamic models developed for those systems to be extended to block-like polyolefins.
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    Polymer Engineering and Science 35 (1995), S. 52-63 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Relationships between the rheological, morphological, and tensile properties of an immiscible blend of 25 wt% of a thermotropic liquid crystalline polymer (LCP) with polycarbonate are presented. The shear viscosity of the blend is intermediate between the two constituent materials, and indicates immiscibility in the melt. Extrudate swell behavior is examined and found to be closely related to that of polycarbonate. The morphology of the dispersed LCP phase varies between droplets and oriented fibrils, and is highly correlated with changes in tensile properties. Fibrils are associated with increased tensile modulus, and their development is favored in the elongation flow fields present in the spinline and in the die convergence section. In all cases, blend stiffness is less than that predicted for a continuous fiber-reinforced composite. Enhanced tensile modulus is associated with both extrusion from shorter length dies and increases in spinline draw ratio, with the latter proving the most important in fibril formation.
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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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  • 58
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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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    Polymer Engineering and Science 35 (1995), S. 129-136 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Instrumented impact testing and analysis were performed on an interlaminartoughened carbon fiber epoxy composite (Toray 3900-2/T800H) and a conventional (untoughened) epoxy composite (Fiberite 934/T300). Severity of impact was varied by using a wide range of impact energy. The effect of difference in the tup of the impact instrument was discussed. The residual compressive strengths after compact (CAI's) were measured by using a universal mechanical tester. The impact damage and delamination resistance of the toughened and conventional composites were quantitatively compared. At the same impact energy, the extent of damage was much less severe and the CAI was higher for the toughened composite. Relationships between the CAI's, the state of impact damage, and impact energy were investigated. Impact damage mechanisms for these two composites were not exactly the same. The impact damage of the conventional composite exhibited much greater extents of delamination. By contrast, interlaminar delamination in the toughened composite was found to be significantly suppressed, and the impact damage was more dominated by controlled matrix cracking/fiber damage, instead of catastrophic delamination. As a result, the CAI's of the toughened composite exhibited a monotonous decrease with increase in the impact energy and in the linear dimension of extents of damage.
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    Polymer Engineering and Science 35 (1995), S. 151-156 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thermal diffusivity of high density polyethylene (HDPE) was studied over a wide range of temperatures (25 to 200°C) by melting powdered HDPE in a cylindrical mold at several pressures (101.3 to 5065 KPa gage) and recording the temperature profiles at several radial positions. The energy equation was solved numerically for cylindrical geometry. The thermal diffusivity of HDPE was fit as a function of temperature, porosity, and pressure.
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    Polymer Engineering and Science 35 (1995), S. 170-172 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 communication is a theoretical re-examination of the model proposed by Choe and Lee for the nonisothermal crystallization kinetics of semicrystalline polymers.
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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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  • 63
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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: 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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    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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    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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  • 66
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    Notes: Mechanical properties of polymers can be described by their stress/strain curves and by their behavior under dynamic mechanical thermal analysis (DMTA). The purpose of this paper is to report such mechanical properties for two unsaturated polycarbosilanes: poly(1, 1-dimethyl-1-sila-cis-pent-3-ene) (I) and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) (II). Tensile strength, elongation at break, modulus, bending modulus, Tg, and tan δ for I, II and for sulfur crosslinked I and II have been measured. The influence of polymer molecular weight, quantity of crosslinking agent, cure time, presence of carbon black filler, the effect of crosshead speed, and frequency on these properties was investigated.
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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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    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. 195-201 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Using low conversion bulk copolymerization experimental data and the apparent rate constant model, the monomer chain cross-transfer rate constants and the cross-termination coefficient were evaluated. It was found that the dependence of the cross-termination coefficient on composition is a function of initiator efficiency and that monomer chain cross-transfer rate constant are relevant for the theoretical estimation of the molecular weights and molecular weight distributions.
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    Polymer Engineering and Science 35 (1995), S. 202-210 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The melt viscosity of thermoplastic starch has been investigated as a function of temperature, moisture content, and processing conditions. The effects of various low molecular weight additives have also been studied. Starch melts exhibit power law behavior over the range of shear rates studied. Melt viscosity decreased with increasing temperature and moisture content (MC). The power law index m increased with increasing temperature. The consistency K decreased with increasing temperature and increasing moisture content. Moisture content during the pelletizing step influenced melt viscosities measured after equilibration to different MCs. All additives studied except glycerol monostearate (GMS) significantly lowered the melt viscosity of starch, some more effectively than water relative to starch with 15% MC. Starch with GMS had viscosities essentially the same as, or slightly higher than, starch/water. This behavior may be due to the presence of unmelted helical inclusion complexes of starch and GMS. Starch formulations at 160°C exhibited melt visocosities similar to an LDPE of melt index 1.8.
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    Polymer Engineering and Science 35 (1995), S. 289-290 
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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
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    Polymer Engineering and Science 35 (1995), S. 291-303 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The phenomenology of yield in bisphenol-A polycarbonate is explored through tensile tests on thin rectangular specimens and through pressure-induced bulging of thin, clamped circular disks. In a tensile test, while the nominal critical stress at which yield initiates and the nominal draw stress at which a stable neck propagates along a specimen depend on the temperature and the strain rate, the ratio of the draw stress to the critical stress is shown to be approximately 0.75 over a temperature range of 22 to 65°C and strain-rates in the range of 10-4 to 100 s-1. Specimens subjected to constant tensile loads between the draw and critical stresses are shown first to creep till stretches on the order of 1.06 are attained and then are shown to undergo stable necking. Tensile tests on thin, wide rectangular specimens show that yielding initiates through shear bands that broaden and intersect to generate necks, which subsequently propagate along the specimen. In pressure-induced bulging of clamped disks, biaxial stretching progresses monotonically under increasing pressures; strain localization does occur near the outer edges of the specimens, however. Heating of a specimen with a substantial stably necked region shows that the temperature-induced recovery of the specimen from its deformed state begins well below the transition temperature Tg of the material, although most of the recovery occurs at Tg.
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    Polymer Engineering and Science 35 (1995), S. 317-330 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of poly(etherether ketone) (PEEK) were subjected to large plastic deformations under uniaxial tension and simple shear by means of a new video-controlled testing method at constant true strain rate. The “equivalent” stress-strain curves obtained under the two loading modes are close at the yield point, but diverge drastically at large strains, with a rapidly increasing hardening in tension and a moderate hardening under simple shear. X-ray diffraction goniometry shows that these contrasting behaviors are associated with the different textures developed in the crystallite orientations. Under tension, the PEEK lamellae are progressively tilted in such a way that the chain axis becomes oriented parallel to the tensile axis; in the other mode, the final chain orientation is near to the shear axis. DSC analyses of deformed samples in both modes are carried out. The results show that the tension loading induces a fragmentation of the thin lamellae, while the shear mode generates less fragmentation. A quantitative model is presented that involves a composite approach: (i) the viscoplastic deformation of the crystalline lamellae, which is controlled by chain slip and transverse slip systems on planes parallel to the c axis, and (ii) the hyperelastic deformation of the amorphous phase, which depends on the affine unfolding of statistically distributed subchains. A discussion of the influence of the CRSS values on the stress-strain curves and textures is developed by means of this model.
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    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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    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. 385-386 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 35 (1995), S. 403-410 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Aging experiments using the NIST (National Institute of Standards and Technology) torsional dilatometer have been performed in which the temperature of an isothermally equilibrated epoxy glass was abruptly changed to a new temperature T0 and the evolution of the volume and torsional relaxation responses recorded. The results of down-jump and up-jump experiments were found to differ dramatically. Not only is the normal asymmetry of volume approach to equilibrium found, but the mechanical responses are found to evolve differently from the volume response, contrary to simple free volume models of the physical aging process. It is found that the torsional modulus changes with increasing time after the T-jump. In the case of the down-jump the evolution of the modulus ceases prior to that of the volume of the sample. In the up-jump experiment, the contrary is true, viz., the modulus continues to evolve after the volume has attained its equilibrium value. The implications of this for the description of material behavior are discussed.
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    Polymer Engineering and Science 35 (1995), S. 395-402 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 statistical theory of the birefringence of an individual non-Gaussian elastomer chain is used together with a chain network description of rubber elasticity to develop a relationship among the strain, birefringence, and stress in elastomers, valid for large deformations under generalized strain states. The result is a fully three-dimensional internal variable based constitutive model of rubber elasticity in which measurement of the elastomeric birefringence during straining in one deformation state characterizes the optically anisotropic response of the elastomer. Simultaneous measurement of the stress vs. strain response provides the rubbery modulus and limiting network extensibility properties needed to completely characterize the mechanical anisotropy of the material. Once characterized using the single, large deformation experiment, the birefringence and stress responses of the elastomer in other deformation states may then be predicted without adjusting any model parameters. The theory is compared to experimental studies from the literature of large strain deformations of elastomers in uniaxial tension and compression for which the exhibited birefringence and stress responses of deforming elastomers have been simultaneously recorded.
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    Polymer Engineering and Science 35 (1995), S. 387-394 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rigid, closed-cell, polyurethane foam consists of interconnected polyurethane plates that form cells. When this foam is compressed, it exhibits an initial elastic regime, which is followed by a plateau regime in which the load required to compress the foam remains nearly constant. In the plateau regime, cell walls are damaged and large permanent volume changes are generated. As additional load is applied, cell walls are compressed against neighboring cell walls, and the stiffness of the foam increases and approaches a value equal to that of solid poyurethane. When the foam is loaded in tension, the cell walls are damaged and the foam fractures. A constitutive theory for rigid polyurethane foam has been developed. This theory is based on a decomposition of the foam in two parts: a skeleton and a nonlinear elastic continuum in parallel. The skeleton accounts for the foam behavior in the elastic and plateau regimes and is described using a coupled plasticity with continuum damage theory. The nonlinear elastic continuum accounts for the lock-up of the foam due to internal gas pressure and cell wall interactions. This new constitutive theory has been implemented in both static and dynamic finite element codes. Numerical simulations performed using the new constitutive theory are presented.
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    Polymer Engineering and Science 35 (1995), S. 426-431 
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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: The nonlinear fracture behavior of polycarbonate is investigated. The feasibility of measurement of the J integral through the optical method of reflected caustics is demonstrated. Significant increase in the crack growth resistance during small amounts of crack extension is observed.
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    Polymer Engineering and Science 35 (1995) 
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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
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    Polymer Engineering and Science 35 (1995), S. 432-440 
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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: Microllular plastics are cellular polymers characterized by cell densities greater than 109 cells/cm3 and cells smaller than 10 μm. One of the critical steps in the continuous production of microcellular plastics is the promotion of high cell nucleation rates in a flowing polymer matrix. These high nucleation rates can be achieved by first forming a polymer/gas solution followed by rapidly decreasing the solubility of gas in the polymer. Since, in the processing range of interest, the gas solubility in the polymer decreases as the pressure decreases, a rapid pressure drop element, consisting of a nozzle, has been employed as a continuous microcellular nucleation device. In this paper, the effects of the pressure drop rate on the nucleation of cells and the cell density are discussed. The experimental results indicate that both the magnitude and the cell density are discussed. The experimental results indicate that both the magnitude and the rate of pressure drop play a strong role in microcellular processing. The pressure phenomenon affects the thermodynamic instability induced in the polymer/gas solution and the competition between cell nucleation and growth.
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    Polymer Engineering and Science 35 (1995), S. 441-459 
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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: The steady melting of several amorphous and semicrystalline polymers during spin welding is analyzed by solving a simplified set of momentum and energy balance equations, assuming a shear-rate and temperature-dependent viscosity. A numerical model is developed for predicting the flow field and the temperature distribution in the molten film. It is shown that the steady melting rate of the thermoplastic solid is affected by the variable viscosity, by the pressure applied on the parts to be joined, and by a balance between the viscous heat generation in the melt and the convection of colder material into the molten film. The convection of heat in the outflow direction is shown to have a much smaller effect on the melting process.
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  • 84
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 477-482 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Glassy shell-rubbery core polymer particles, 0.1 to 0.2 μm in diameter, increase the plane strain JIC values of 3.175 mm thick polycarbonate from 3.05 kJ/m2 (no particles) to 9.5 kJ/m2 (7.5 phr particles) at 23°C. Some modest decreases in these values are caused by tests at -20°C in samples 9.525 and 3.175 mm thick. If only the particle concentration is varied, JIC increases monotonically to 7.5 phr (by wt), then levels off or decreases slightly at 10.0 phr. The total volume of 1 to 2 μm diameter cavities formed in the matrix by the apparently unbonded particles behaves similarly; cavity volume and JIC are directly related. With increasing particle concentration the tensile modulus is unchanged, the yield stress and strain decrease modestly, the strain at fracture decreases appreciably, and the heat recoverable orientation in the fractured samples decreases. Few cavities are formed. The particles reduce the extent of shear deformation in the tensile samples.
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  • 85
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 483-492 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model for a laser-induced photopolymerization process has been developed. This model simulates important aspects of stereolithography, a rapid prototyping process used for the production of three-dimensional plastic parts. The model consists of a set of coupled partial differential equations and considers irradiation, chemical reaction, and heat transfer in a small zone of material exposed to a stationary UV laser source. Numerical techniques are used for an approximate solution of the model equations, and the output includes spatial and temporal variations in the conversion of monomer to polymer, depletion of photoinitiator, and local variations of temperature in and around the region contacted by the laser light. Maximum conversions of approximately 60% and peak temperature rises of approximately 35° C were calculated for the cylindrical exposed region. Results have provided insights concerning laser dwell time, depth penetration, and the uniformity of polymer formed during the stereolithography process.
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  • 86
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 499-505 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The deformation of three types of sulfone polymers - polysulfone (PSF), poly(ether sulfone) (PESF), and polyarylsulfone (PASF) - was performed with a mechanical testing system (MTS). The result and samples were studied using a transmission electron microscope (TEM), a dynamic mechanical analyzer (DMA), and a dielectric thermal analyzer (DETA). Stripes on TEM micrographs for small deformations increase with the fracture toughness (GIc). The activation energy (Ea) of the α-transition was determined from DETA. The results show that both Ea and TEM micrographs can be used to qualitatively estimate the order of GIc of sulfone polymers. An energy model was proposed to explain this phenomenon.
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  • 87
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 419-425 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We investigate criteria for craze failure at a crack tip and the dependence of craze failure on the molecular weight of the polymer. Our micromechanics model is based on the presence of cross-tie fibrils in the craze microstructure. These cross-tie fibrils give the craze some small lateral load bearing capacity so that they can transfer stress between the main fibrils. This load transfer mechanism allows the normal stress on the fibrils directly ahead of the crack tip in the center of the craze to reach the breaking stress of the polymer chains. We solve for stress field near the crack trip and use it to relate craze failure to the external loading and microstructural quantities such as the craze widening (drawing) stress, the fibril spacing, the molecular weight, and the force to break a single polymer chain. The relationship between energy flow to the crack tip due to external loading and the work of local fracture by fibril breakdown is also obtained. Our analysis shows that the normal stress acting on the fibrils at the crack tip increases linearly as the square root of the craze thickness, assuming that the normal stress distribution is uniform and is equal to the drawing stress acting on the craze-bulk interface. The critical crack opening displacement, and hence the fracture toghness is shown to be proportional to [1-(Me/qMn)]2, where Me is the entanglement molecular weight, Mn is the number average molecular weight of polymer before crazing, and q is the fraction of entangled strands that do not undergo chain scission in forming the craze.
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  • 88
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 471-476 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 JIC values for core-shell-particle-toughened polycarbonate were determined at different temperatures and at 0, 2.5, 5.0, 7.5, and 10.0 phr particle content by six similar methods, using compact tensile specimens. At the 2.5 phr toughener level, the JIC values ranged from 2878 to 6100 J/m2, and at 7.5 phr, they ranged from 6125 to 10,760 J/m2, dependent only upon how the same JI-Δ a data were interpreted. This indicates that more work will be required before a reliable method of JIC measurement that can be applied to tough polymers is achieved.
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  • 89
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 461-470 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Stoichimetric mixtures of a diglycidyl ether of bisphenol A (DGEBA)/ diaminodiphenyl sulfone (DDS) and a DGEBA/meta phenylene diamine (mPDA) were cured using both microwave and thermal energy. Fourier transform infrared (FTIR) was used for the measurement of the extent of cure and thermal mechanical analysis (TMA) was used for the determination of the glass transition temperature (Tg). The cure kinetics of the DGEBA/mPDA and DGEBA/DDS systems were described by an autocatalytic kinetic model up to vitrification in both the microwave and thermal cure. For the DGEBA/mPDA system, the reaction rate constants of the primary amine-epoxy reaction are equal to those of the secondary amine-epoxy reaction, and the etherification reaction is negligible for both microwave and thermal cure. For the DGEBA/DDS system, the reaction rate constants of the primary amine-epoxy reaction are greater than those of the secondary amine-epoxy reaction and the etherification reaction is only negligible at low cure temperatures for both microwave and thermal cure. Microwave radiation decreases the reaction rate constant ratio of the secondary amine-epoxy reaction to the primary amine-epxy reaction and the ratio of the etherification reaction to the primary amine-epoxy reaction. Tg data were fitted to the DiBenedetto model. A master curve and a time-temperature-transformation (TTT) diagram were constructed. The vitrification time is shorter in microwave cure than in thermal cure, especially at higher isothermal cure temperatures. For the DGEBA/mPDA system, the minimum vitrification time is two to five times shorter in the microwave cure than in the thermal cure. For the DGEBA/DDS system, the minimum vitrification time is 44 times shorter in the microwave cure than in the thermal cure.
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  • 90
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 493-498 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical process model that stimulates important aspects of stereolithography, a rapid prototyping technique used for the production of three-dimensional plastic parts, has been developed. The model consists of a set of coupled partial differential equations and considers irradiation, chemical reaction, and heat transfer in a vat of photomonomer exposed to a moving UV laser source. Laser motion occurs in a straight line (vector path), and the model thus simulates the production of a single strand of plastic. Numerical techniques are used for approximate solution of the model equations, and output includes spatial and temporal variations in conversion of monomer to polymer, depletion of photoinitiator, and variations of temperature along the line of exposed material. The formation of a temperature wave that moves along the line of plastic is observed, together with the fact that the leading edge of the wave is steeper than the trailing edge, i.e., the material heats considerably faster than it cools. The maximum temperature of the wave reaches a pseudo-steady state after a short time. The results have provided useful information concerning the temperature at which the majority of the polymerization occurs; provided information on overall transient temperature behavior; allowed computer prediction of stereolithography working curves (cure depth and cure width vs. laser scan rate); and afforded a means for evaluating the amount of reaction that occurs in the dark period after light exposure.
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  • 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: 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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  • 92
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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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  • 93
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 94
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 95
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 96
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 97
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 619-636 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 phase morphological development under different extrusion conditions was studied in terms of the rheological property and interfacial tension of various elastomers and thermoplstics. The interfacial tension for elastomers and thermoplastics was investigated by using a breaking thread method (1-4). We found that the method is suitable for measuring interfacial tension without degradation. The droplet-fibrillation transition phenomenon was observed in various extrudates of fluoroelastomer/polycarbonate blends. The criteria for the flow-induced morphology, in particular the droplet-fibrillation transition, are critically discussed in this paper.
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  • 98
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 637-641 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Results of measurements of the electrical conductivity of low density polyethylene/polypyrrole and polystyrene/polypyrrole composites are reported. It is observed that the electrical conductivity of the composite vs. concentration follows the power law predicted by the percolation theory. The manufacturing process influences the homogeneity of the composite at microscopic scale and thus the percolation threshold. Annealing studies show that the stability of the electrical conductivity of the composite is related to the thermal expansion of the polymers and the relaxation of the polymer chains. The decrease of the electrical conductivity of the composite is attributed to the interruption of the percolation path.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 648-657 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley 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 compatibilizing effect of a polystyrene-hydrolyzed poly(t-butyl acrylate) diblock copolymer (SBAH) on the phase structure, rheological properties, and mechanical properties of immiscible poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and polyamide-6 (PA) blends was investigated. The SBAH was prepared by sequential anionic polymerization of styrene and t-butyl acrylate, followed by acid-catalyzed hydrolysis of t-butyl acrylate block. Scanning electron micrographs show that the blends exhibit a more regular and finer dispersion when the SBAH of 47% hydrolyzed t-butyl acrylate block is added. By addition of small amount of the block copolymer, the blends show non-Newtonian power-law behavior, and the contribution of storage modulus (G′) to the total response increases. Solubility tests support the formation of graft copolymer by chemical reaction between amine groups of the PA and carboxyl groups of the SBAH. Both modulus and strength are improved about 20% with addition of the 3 wt% SBAH, while the elongation at break decreases notably; thus, the blends fail in a brittle manner.
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  • 100
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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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