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  • Physics  (5,775)
  • 1995-1999  (576)
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  • 1
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    Amsterdam ; New York : North-Holland Pub. Co
    Keywords: DDC 530.1 ; LC QC20 ; Mathematical physics ; Physics ; Quantum theory ; Relativity (Physics)
    ISBN: 9780444875853
    Language: English
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: polynorbornene ; gas separation ; membranes ; permeation ; sorption ; ring-opening metathesis polymerization ; ROMP ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Advances in the field of membrane gas separation over the past decade have encouraged the search for even better polymers and membranes for gas separation. They also have motivated studies on the relationship between the structure and the gas transport properties of different classes of polymers. Interest has recently been demonstrated in the literature in norbornene polymers with different side groups. These polymers can easily be prepared via ring-opening metathesis polymerization (ROMP) of norbornene (bicyclo[2.2.1]hept-2-ene) derivatives. So far, information on the microstructure of the polymers is scarce, so little is known about the influence of stereochemistry and tacticity of the polymer on gas separation properties. In this work, we present gas permeability and selectivity data for stereoregular unsubstituted polynorbornene. It will be shown that a high order of tacticity has a positive effect on both permeation and separation results. © 1997 John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: europium methacrylate ; ionomers ; fluorimetry ; differential scanning calorimetry ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorimetry and differential scanning calorimetry have been used to characterize ionomers that were synthesized by copolymerization of methyl methacrylate, methacrylic acid, and europium methacrylate (EMA). Under excitation of UV light at 375 nm no self-quenching was found in fluorescence of EMA-containing ionomers at 615 nm within the Eu3+ concentration range of 1.6 × 10-2 to 11.49 × 10-2 mol %, which means that the distance between two Eu3+ ions is larger than 50 Å. In the same concentration range self-quenching took place in europium octanoate (EOA)-containing ionomers in which EOA was doped as an additive. Only one Tg was found for both kinds of polymers within the concentration range of Eu3+ ions. For all ion contents studied, Tg values were essentially independent of ion content and values were slightly higher for the EMA containing ionomers. © 1997 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: epoxy resin ; poly(ether sulfone) ; physical aging ; DSC ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The physical aging process of 4,4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with poly(ether sulfone) (PES) was studied by differential scanning calorimetry (DSC) at four aging temperatures between Tg-50°C and Tg-10°C. At aging temperatures between Tg-50 and Tg-30°C, the experimental results of epoxy resin blended with 20 wt% of PES showed two enthalpy relaxation processes. One relaxation process was due to the physical aging of PES, the other relaxation process was due to the physical aging of epoxy resin. The distribution of enthalpy relaxation process due to physical aging of epoxy resin in the blend was broader and the characteristic relaxation time shorter than those of pure epoxy resin at the above aging temperatures (between Tg-50 and Tg-30°C). At an aging temperature between Tg-30 and Tg-10°C, only one enthalpy relaxation process was found for the epoxy resin blended with PES, the relaxation process was similar to that of pure epoxy resin. The enthalpy relaxation process due to the physical aging of PES in the epoxy matrix was similar to that of pure PES at aging temperatures between Tg-50 and Tg-10°C. © 1997 John Wiley & Sons, Inc.
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  • 5
    ISSN: 0887-6266
    Keywords: polyoxymethylene ; elastomer blend ; drawn fibers ; mechanical properties ; structure relationships ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Superdrawn fibers of an elastomer-poly(oxymethylene) (POM) blend have been prepared and investigated in terms of the structure and mechanical properties. The development of the mechanical properties along the fiber axis and the formation of a higher order structure during drawing were slightly retarded by blending, but the loop tenacity increased greatly with the elastomer content. The blend microtextures had an immiscible and phase-separated morphology in which the elastomer was dispersed in the form of streaks between the oriented POM layers, which allowed the fiber to split into smaller filaments on bending. The high loop tenacity of the blend fibers is due to an increase in the radius of curvature resulting from the filament splitting on bending, because the shear stress at the bending corner becomes higher as the radius of curvature increases. © 1997 John Wiley & Sons, Inc.
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  • 6
    ISSN: 0887-6266
    Keywords: syndiotactic polystyrene ; polymorphism ; chloroform ; clathration ; sorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The analysis of chloroform vapor sorption at 35°C in semicrystalline syndiotactic polystyrene samples shows remarkably different sorption isotherms, depending on the crystalline form of the samples. In particular, “emptied” clathrate (“emptied” δ form) samples are characterized by higher equilibrium sorption levels and the differences are particularly relevant for low vapor activities. Moreover, sorption kinetics detected at a vapor activity equal to 0.5 show that in the case of “emptied” δ form samples the sorption rate is much higher than for the other semicrystalline samples. The larger sorption equilibrium uptakes and sorption rates of the “emptied” δ form samples are essentially due to their ability to absorb chloroform, already for low activities, by clathration in the crystalline phase. The measured equilibrium uptakes and sorption kinetics suggest that “emptied” δ form samples of syndiotactic polystyrene could be suitable for removing polluting chlorinated compounds from vapor and liquid streams. © 1997 John Wiley & Sons, Inc.
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  • 7
    ISSN: 0887-6266
    Keywords: PMSP ; copolymer and blend ; aging ; gas permeability ; molecular motion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The poly(1-trimethylsilyl-1-propyne) (PMSP) has the potential to be an important membrane gas separation material due to the fact that it has the highest gas permeability of all polymeric membranes. One problem with PMSP is a decrease in the gas permeability with age. In order to understand the aging processes, we studied the change in free volume and the molecular motions of the PMSP and its membranes modified with 1-phenyl-1-propyne (PP) structures; that is, a copolymer and a blend of PMSP and PPP. During aging, the unrelaxed volume of the PMSP membrane was relaxed, and the molecular motion of carbons dropped, suggesting that the decrease in the microvoids caused a tighter chain packing. The copolymer and blend membrane had stable permeability compared to the PMSP. In particular, the addition of a small amount of the PP structure provided excellent stability with high gas permeability. A decrease in the unrelaxed volume of modified membranes was hardly observed with age; however, the molecular motion of some carbons slightly changed. This change did not affect the gas permeability. In this case, a larger unrelaxed volume was probably a dominant factor in the gas permeation of the PMSP rich membranes relative to the molecular motion in the T1 measurement. © 1997 John Wiley & Sons, Inc.
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  • 8
    ISSN: 0887-6266
    Keywords: Asymmetric star polystyrenes ; star polymers ; solution properties ; size exclusion chromatography ; light scattering ; viscometry ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sequential anionic polymerization of styrene and divinylbenzene (DVB) is known to lead to the formation of star-shaped polymers. This ‘arms-first’ method has been widely used and studied. It is known that this polymerization forms stars with anionically active cores. This article is concerned with the attempt to make asymmetric-star polymers utilizing these living carbanionic sites present in the core to form a second set of shorter arms growing out from the star core. The presence of remaining unreacted DVB within the core was found to cause the stars to couple to form linked double stars and other larger structures. Results from detailed dilute solution studies of the resulting polymers are reported. It was found that the results obtained from size exclusion chromatography for the double stars were flow rate dependent; only at low flow rates was a true size separation obtained. © 1997 John Wiley & Sons, Inc.
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  • 9
    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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  • 10
    ISSN: 0887-6266
    Keywords: polythiophene ; polypyrrole ; electropolymerization ; dopant anion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pyrrole, thiophene, and a mixture of the two monomers were electrochemically polymerized to investigate polymerization rates and the morphology change of the polymer matrix, and to improve the aging and cyclic voltammetric behaviors of the polymers. Thiophene was polymerized on a smooth surface of Pt electrode by two steps. The first step was controlled by electron transfer at the electrical double layer and the other by diffusion of the monomer reacting on the immobilized layer consisting of the precoated thiophene polymer. The electropolymerization rate of the second step was 1.85 × 10-4 cm3 mol-1 s-1, which is faster by 8.63 × 102 times than the first step. Some supporting electrolytes such as KPF6, LiClO4, TBAP, and TBABF4 were employed in the polymerization reaction to see the effects of dopant anions on the polymerization rate, and KPF6 was the fastest one at 2.41 × 10-6 cm s-1. However, owing to its sensitivity to oxygen, LiClO4 was used for the polymerization that is fairly stable in air and the same rate as KPF6. For the competitive polymerization reaction of the two monomers the rate of thiophene was found to be about 11 times slower than that of thiophene alone. When the starting concentration of the thiophene monomer was higher than pyrrole by five times, its portion in the composite polymer was found to be only 8-10%. However, this level gave desirable results in terms of redox properties and aging. The resistance against aging was explained by the morphology change, which came from great shrinking of its porosity. © 1997 John Wiley & Sons, Inc.
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  • 11
    ISSN: 0887-6266
    Keywords: coagulation ; low dielectric constant ; fiber ; miscibility ; morphology ; solution spinning ; polyimide ; precipitation strength ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Control of the internal morphology of wet-spun fibers from a fluorinated polyimide has been achieved by varying the rate of polymer coagulation through adjustments in nonsolvent/solvent miscibility and precipitation strength of the coagulation bath. Filament internal morphologies ranged from very porous or sponge-like to fully solid. Intermediate structures included fibers containing a spongy core with a nonporous skin, sponge-like fibers containing large voids, and a relatively solid material containing randomly spaced small voids. The cross-sectional shape of the fiber is dependent upon the coagulation process as well as the volume contraction of the initial extrudate. Drawn fibers (3×) retained the original asspun cross-sectional shape and also lost porosity. Mechanical properties of poly(6FDA-4BDAF) fibers have an inverse relationship to filament porosity. Maximum modulus and break strength for drawn fibers is approximately 6 CPa and 200 MPa, respectively. Asspun mechanical properties were dependent upon the processing conditions and have moduli between 0.4-3.0 Gpa and break strengths of 10-160 MPa. A dielectric constant of 2.50 for nonporous films was measured over a frequency range between 1.0 MHz to 1.8 GHz, showing little dispersion. © 1997 John Wiley & Sons, Inc.
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  • 12
    ISSN: 0887-6266
    Keywords: SALS ; polymer ; crystallization kinetics ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 13
    ISSN: 0887-6266
    Keywords: neutron diffraction ; X-ray diffraction ; poly(vinyl alcohol) ; rigid-body least-squares method ; difference synthesis ; intramolecular hydrogen bond ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Different crystal structure models have been proposed for atactic poly(vinyl alcohol) by two groups: Bunn and Sakurada et al. The models differ principally in the azimuthal angle of the planar zigzag backbone and the hydrogen bonding network. In the present study, reexamination of the crystal structure analysis was carried out by using both the X-ray and neutron diffraction methods. The crystal structure model proposed by Bunn is found to be superior. The (Fo - Fc) synthesis was made for the neutron data (100 K), in which the hydrogen atoms to be associated with the hydrogen bonds are not incorporated into Fc calculation. On the map, three peaks were found, which may be attributed to the hydrogen atoms to be associated with the intramolecular hydrogen bonds between OH groups in an isotactic sequence and the two kinds of intermolecular hydrogen bonds. © 1997 John Wiley & Sons, Inc.
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  • 14
    ISSN: 0887-6266
    Keywords: photoacoustic spectroscopy ; polyvinyl alcohol and rare earths ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoacoustic (PA) spectra of Ho3+, Er3+, and Sm3+ doped PVA films were obtained in 350-800 nm range. PA spectra were also obtained for the respective dopant oxides: Ho2O3, Er2O3, and Sm2O3 for comparison. It was found that in PVA the PA sensitivity has increased considerably compared to pure rare earth oxides. The relative intensities of absorption bands at 540 and 637 nm of Ho3+: PVA have shown distinct enhancement, indicating the increase in nonradiative relaxation at these excitations. Furthermore, the PA signals at wavelengths for different PA absorption bands were monitored as a function of chopping frequency. These experiments have shown that PA signal varies w-1 both for oxides and PVA samples, suggesting that they behave as thermally thin samples. © 1997 John Wiley & Sons, Inc.
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  • 15
    ISSN: 0887-6266
    Keywords: poly(ester-imide)s ; liquid crystalline polymers ; dielectric relaxation ; model calculations ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two different series of poly(ester imide)s, which are distinguished from each other in the orientation of the ester linkages and show well-differentiated thermotropic behavior, are investigated by means of model calculations and dielectric relaxation spectroscopy. Model calculations show that the orientation of the ester linkages has a strong influence on the rotational energy barriers. The dielectric relaxation spectra of both series shows three relaxation regions in the temperature range between 100 and 400 K that have been identified as the α-, β- and γ-relaxation processes. A difference of about two orders of magnitude between the characteristic rates of the γ-relaxation is the main feature observed in the dielectric response. However, the β-relaxation shows very similar behavior for both series. The differences in the relaxation behavior in the solid state are interpreted on the basis of the rotational barriers deduced from the model calculation results. © 1997 John Wiley & Sons, Inc.
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  • 16
    ISSN: 0887-6266
    Keywords: stress-strain ; yield ; crystallite ; ethylene copolymer ; superstructure ; lamellae ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nominal stress-strain curves of a series of random ethylene-hexene copolymers having narrow composition and most probable molecular weight distributions were investigated. A series of such molecular weight copolymers with a constant concentration of branches were crystallized under a variety of conditions. In each molecular weight series the level of crystallinity was approximately constant. Particular attention was focused on the yield region and the nature of the yielding process. It was found, quite surprisingly, that the yield stress was not solely dependent on the crystallinity level. Moreover, the shape of the force-elongation curve in the yield region was very dependent on the molecular weight and the crystallization mode. These changes in yielding correlated quite well with the overall crystallite structure that was characterized by thin section transmission electron microscopy. The orthorhombic unit cell of polyethylene was maintained in all the samples despite the changes that occurred in the overall crystallite structure. © 1997 John Wiley & Sons, Inc.
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  • 17
    ISSN: 0887-6266
    Keywords: polyurethane ionomer ; transesterification ; morphology ; phase compatibility ; ionic cluster ; solid-state ionic conductivity ; single ion transport mechanism ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polyether (PTMO, PEO) polyurethane ionomers having different contents of sodium sulfonate groups in the soft segments have been synthesized. The reaction of transesterification was involved in the incorporation of the sodium sulfonate groups in the polyether. The polyurethane ionomers were characterized by means of dynamic mechanical thermal analysis, differential scanning calorimetry, and small-angle x-ray scattering. Solid-state ionic conductivity was also measured. As the ionization level increased, the compatibility of the hard and soft segments increased and the glass transition region of the soft segment became broader. These samples had relatively higher moduli and good film-forming ability. Moreover, this kind of ionomer provides a very promising ionic conductive multiphase polymer with a single ion transport mechanism. © 1997 John Wiley & Sons, Inc.
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  • 18
    ISSN: 0887-6266
    Keywords: isotactic polypropylene ; propylene/ethylene copolymers ; injection molding ; SCORIM ; mechanical properties ; impact testing ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The aim of the research reported in these two articles was to explore the relationship between processing conditions and the physical properties of different grades of isotactic polypropylene injection moldings and propylene/ethylene copolymers. This first article describes the methods and processing conditions used for molding, together with mechanical test results. Both conventional and shear-controlled orientation injection molding (SCORIM) have been employed for the production of moldings. SCORIM is based on the application of specific macroscopic shears to a solidifying melt, which in turn, facilitates enhanced molecular alignment. SCORIM results in more pronounced molecular orientation than conventional injection molding, which is consistent with the substantial increase in Young's modulus of moldings produced by SCORIM. By controlling the processing parameters it is possible to control and enhance the stiffness without loss of tensile strength. An increase of up to four times in impact strength has been achieved with SCORIM as well as a substantial increase in Young's modulus. The conventional injection moldings containing pronounced molecular orientation exhibited impact resistance well below that for the SCORIM moldings. The mechanical tests carried out at 80°C showed that the high-temperature mechanical properties of all the materials, converted into moldings using SCORIM, exhibited substantial enhancement when compared with moldings of the same material converted by conventional injection molding. © 1997 John Wiley & Sons, Inc.
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  • 19
    ISSN: 0887-6266
    Keywords: isotactic polypropylene ; injection molding ; SCORIM ; γ-phase ; shish-kebab morphology ; molecular alignment ; crystallinity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preceding article referred to the processing of various grades of isotactic polypropylene (iPP) and propylene/ethylene copolymers by conventional and shear-controlled orientation injection molding (SCORIM), and considered the mechanical properties of the molded polymers in relation to the processing conditions applied. This article is principally concerned with the morphology and phase relationships that apply in injection-molded iPP. The γ-phase of isotactic polypropylene is reported to occur in moldings with pronounced molecular orientation. The presence of γ-phase in injection moldings is indicative of enhanced Young's modulus, and tensile strength provided that the melt has not been subjected to excessive deformation during processing. The common view that isotactic polypropylene exhibits only α- and β-phases in commercially produced moldings is challenged. SCORIM moldings contain less β-phase than conventional moldings, and exhibit greater overall crystallinity than moldings produced by conventional methods. The difference in the relative proportions of α-, β-, and γ-phases is marked and depends on processing conditions and the molding method. Shear-controlled orientation injection molding (SCORIM) results in more pronounced molecular orientation than conventional injection molding, which is consistent with the substantial increase in Young's modulus of moldings produced by SCORIM. The improved mechanical properties of iPP moldings is attributed to shish-kebab morphology developed by the action of shear to the solidifying melt. A new model is proposed for the oriented region morphology in iPP injection moldings based on the results presented in this article. © 1997 John Wiley & Sons, Inc.
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  • 20
    ISSN: 0887-6266
    Keywords: epoxy resins ; liquid modifiers ; cure schedule ; ultimate properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin has been stoichiometrically cured with cycloaliphatic amine 4,4′-diamino-3,3′-dimethylcyclohexylmethane (3DCM) and modified with an amine terminated oligomer polyoxypropylenetriamine (POPTA) at a concentration of 15 wt %. Mixtures, postcured at the same temperature, have been precured at different temperatures. Phase separation takes place before gelation at all precure temperatures used. The variation in the glass transition region of the mixtures has been analyzed by dynamic mechanical measurements. Mechanical properties and fracture toughness of the modified mixtures have been related to their microstructural spherical features. Results are compared to those for the unmodified mixtures cured with different precure temperatures. © 1997 John Wiley & Sons, Inc.
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  • 21
    ISSN: 0887-6266
    Keywords: polymer blends ; morphology ; stability ; co-continuity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological stability of polystyrene high-density polyethylene (PS/PE) blend is investigated in the region of dual-phase continuity. The effect of the addition of a triblock SEBS copolymer to the blends on the stability of these morphologies, is examined. The results show that the morphology of the unmodified blends changes from co-continuous to droplet matrix for PS-rich blends whereas the morphology of a 50/50 blend maintains continuity but coarsened significantly upon annealing at 200°C. In the presence of the copolymer, these morphologies are much more stable. Selective solvent extraction of polystyrene in di-ethyl ether reveals that the level of PS continuity in the 50/50 blend is higher for the unmodified system than for the modified one. Upon annealing, the level of PS continuity significantly increases for the unmodified 50/50 PS/PE blend. The effect of the copolymer content in the blend on the interfacial tension between the two components is also investigated using the breaking thread method. The interfacial tension is found to be reduced from 5.6 to 1.1 mN/m by the addition of 20 parts of the copolymer to the blend. © 1997 John Wiley & Sons, Inc.
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  • 22
    ISSN: 0887-6266
    Keywords: PETI ; ester interchange reaction ; PET/PEI melt blend ; sequence randomness ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Optimum conditions for the synthesis of PEI of considerable molecular weight have been established. Poly(ethylene terephthalate-co-isophthalate) (PETI) has been prepared through the ester interchange reaction of a blend of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI). NMR analysis has indicated that the PETI changes from a block-type copolymer to a random type copolymer as the ester interchange reaction proceeds. If the reaction is limited to 20 min, the resulting PETI is crystallizable. The effects of catalysts that have been used during the synthesis of PEI on the characteristics of PETI are also discussed. © 1997 John Wiley & Sons, Inc.
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  • 23
    ISSN: 0887-6266
    Keywords: PVC ; chain local dynamics ; 13C NMR relaxation ; Kramers' theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon-13 spin-lattice, spin-spin relaxation times, and NOE values were measured as a function of temperature at two magnetic fields for poly(vinyl chloride) (PVC) in three solvents: chloroform, dioxane, and dimethyl sulfoxide. The relaxation data were interpreted in terms of chain local motions by using the bimodal time-correlation function of the Dejean-Laupretre-Monnerie (DLM) model. Using this model, the correlation times obtained in this study, as well as those from an earlier study in dibutyl phthalate and 1,1,2,2-tetrachloroethane did not follow a linear relationship with solvent viscosity. Instead, the chain local dynamics showed a 0.60 power dependence on solvent viscosity, indicating that PVC deviates from the hydrodynamic Kramers' theory. © 1997 John Wiley & Sons, Inc.
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  • 24
    ISSN: 0887-6266
    Keywords: polypyrrole ; electrical conductivity ; composite ; surfaces ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electrically conductive composite surfaces were prepared by a diffusion-controlled in situ polymerization of pyrrole in the surface layer of sulfonated polystyrene ionomer films. Premolded films of the ionomer sulfonic acid derivatives were sequentially immersed in aqueous solutions of pyrrole and FeCl3, and polymerization occurred only where both the monomer and the oxidant were present. The penetration of the polypyrrole (PPy) into the film was controlled by varying the immersion time in the monomer solution. The amount of PPy produced depended on the immersion time of the film in the monomer and the degree of sulfonation of the ionomer. Surface conductivities of 10-4-10-1 S/cm were achieved with PPy concentrations from 2 to 22 wt % and composite layers as thin as 15 μm. Intermolecular interactions occurred between PPy and the ionomer by proton transfer. Incorporation of PPy also increased the tensile strength of the ionomer film, significantly increased its modulus above Tg, and inhibited melt flow. © 1997 John Wiley & Sons, Inc.
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  • 25
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: water ; miscible blends ; sorption ; transport ; polyethersulfone ; polyethyloxazoline ; hydrophilic ; hydrophobic ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Water sorption and transport properties for a series of homogeneous blends of hydrophobic polyethersulfone and hydrophilic polyethyloxazoline are reported. Only blends that remained homogeneous after exposure to liquid water were studied in detail. Equilibrium solubility of water in the blend films increases with increasing hydrophilic polymer content. For all materials, equilibrium sorption isotherms show dual-mode behavior at low water vapor activities and swelling behavior at high activities. The sorption/desorption kinetics for PES are generally Fickian, but two-stage behavior is evident in blends containing 10 and 20% polyethyloxazoline. Diffusion coefficients decrease with increasing polyethyloxazoline content, owing to a decrease in the fractional free volume. For all materials, the diffusion coefficient shows a positive dependence on water vapor activity or concentration due to plasticization of the material by high levels of sorbed water, but it becomes a greater function of activity as the composition of hydrophilic polymer in the blend is increased. Since the decrease in the diffusion coefficient is greater than the increase in the solubility coefficient, the permeability coefficient decreases with increasing hydrophilic polymer content. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 993-1007, 1997
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  • 26
    ISSN: 0887-6266
    Keywords: ethylene-1-hexene copolymer ; polypropylene ; polymer blend ; miscibility ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphology and isothermal growth rates of spherulites for the binary blends consisting of an isotactic polypropylene (i-PP) and an ethylene-1-hexene rubber (EHR) were examined as a function of the crystallization temperature ranging from 388 K to 418 K. In this study, two types of EHR's were employed: “ethylene rich” EHR and “1-hexene rich” EHR. The blends of i-PP with the EHR of 51 mol % 1-hexene are miscible in the molten state, whereas the blends with the EHR of 33 mol % 1-hexene are immiscible in the molten state. It is found that the isothermal spherulite growth rate of the miscible i-PP/EHR blends decreases with increasing the EHR fraction, whereas the spherulite growth rate of the immiscible i-PP/EHR blends is independent of the blend composition and is the same as that of the i-PP. Optical microscope observation of the miscible blends crystallized isothermally shows that there are no rubber domains either in the intraspherulitic or in the interspherulitic contact regions. On the other hand, the immiscible i-PP/EHR blends show a phase-separated morphology. Furthermore, the number of tangential lamellae of the miscible i-PP/EHR blends is found to be increased by blending of the EHR, leading to the spherulite with negative birefringence. The sign of birefringence of spherulites is unaffected by the regime transition as well as by the fold surface free energy. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 953-961, 1997
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  • 27
    ISSN: 0887-6266
    Keywords: carbazole ; excimer ; fluorescence ; migration ; photophysics ; trapping ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Steady-state and time-resolved fluorescence techniques have been used to study the photophysical behaviors of poly(N-vinyl carbazole), PNVCz and a series of N-vinyl carbazole-methyl acrylate (NVCz-co-MA) copolymers in dilute solution as a function of both NVCz composition and temperature. A kinetic scheme, intended to describe intramolecular excimer formation across the entire NVCz composition range, is proposed. In low aromatic content copolymers, two monomer species (unquenched and quenched monomer) and two excimer species (the sandwich-like excimer and a higher energy excimer) exist. The contribution from monomer emission to the overall fluorescence decreases with increasing NVCz content through increased excimer formation: this is likely to be consequent upon (1) an increase in the number of excimer forming sites, and (2) increasing efficiency of energy transfer from the excited monomers to the excimer forming sites. In the homopolymer, PNVCz, the only emission that can be observed on a nanosecond timescale is excimeric. This fluorescence appears to originate from three excimer species (the sandwich-like excimer, and two higher energy forms). For the homopolymer, the current observations are consistent with the model proposed by Vandendriessche and De Schryver [Polym. Photochem. 7, 153 (1986)]. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 963-978, 1997
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  • 28
    ISSN: 0887-6266
    Keywords: confocal fluorescence microscopy ; polymer blends ; polymer interfaces ; compatibilizers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Binary blends of linear low density polyethylene (PE) and polypropylene (PP), and ternary blends of PE, PP, and EP copolymer (EPR) were prepared in a finely mixed state. In all blends the ratio of PP to PE was 85/15. In some of the blends, the PE component was labeled with a fluorescent dye; in other blends, the EPR component was labeled. These blends were investigated by laser scanning confocal fluorescence microscopy [LCFM] as a function of annealing time as well as EPR compatibilizer content. In this way we were able to follow the evolution of sample morphology and the location of the EPR in the blends. The presence of EPR in the blends retards the growth of droplets of the dispersed PE phase. When EPR was added in amounts up to 5 wt %, it tended to cover the PE droplets in patches rather than form a true core-shell structure. In the LCFM images, the EPR/PP interface appeared sharper than the EPR/PE interface. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 979-991, 1997
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  • 29
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 30
    ISSN: 0887-6266
    Keywords: screening length ; clusters ; dynamic light scattering ; melt ; concentrated solutions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic light-scattering measurements have been made on the “soft” polymer: poly(n-laurylmethacrylate) (PLMA) in solution in ethyl acetate over the concentration range 0.1 〈 C 〈 0.9 g/mL as well as melt PLMA. With the concentrated solutions, the hydrodynamic screening length (ξh) scales with an exponent of -0.7 below C ≈ 0.3 g/mL. Importantly, ξh decreases above 0.3 g/mL, and the concentration dependence increases strongly above this concentration. The latter contrasts with the behavior in a variety of well-studied poly(styrene) solutions, which are inevitably investigated close to the glass point, and for which there is a pronounced increase of ξh over the same concentration range. In PLMA solutions, the decrease in ξh parallels the behavior of the static screening length (ξs) which has been observed in other flexible polymer systems.Dynamic “clusters” (also termed “long-range density fluctuations”) contribute a large part of the scattered intensity above the concentration 0.6 g/mL and also in melt PLMA which contrasts with poly(styrene) systems in which they are absent. In common with the clusters recently observed in another polymeric melt, poly(methyl-p-tolylsiloxane) (ref. 9) this component is diffusive. While, however, in the latter system the clusters “melt out” at 90°C, we find in the well-matured PLMA systems that the cluster amplitude is temperature-independent (within the temperature-time range studied) in the solutions up to at least 80°C and up to at least 150°C in the melt, which were the highest temperatures examined. The clusters in the PLMA systems have a correlation length of the magnitude 65 nm in the melt, whereas in the solutions this dimension varies between 73 nm at 0.9 g/mL to 126 nm at 0.7 g/mL. In PLMA the clusters are presumed to arise from local segregation owing to the large paraffinic side groups on the chain. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1013-1024, 1997
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  • 31
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: comb-shaped polymer ; poly(3-dodecyl thiophene) ; poly(octadecyl acrylate) ; electroactive polymer ; chromism ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational mode change of the stiff alkylated polymer, poly(3-dodecyl thiophene) (PDDT), with a flexible comb-like coil poly(octadecyl acrylate) (PODA), and the effect of intermolecular interaction between these two alkylated polymers with different chemical structure of the backbone were investigated using UV-Vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimeter (DSC), and wide-angle x-ray diffraction (WAXD). In addition to the characteristics of thermochromism, a homogeneous one phase was observed above 175°C when the PODA content was 10 wt % or less. Increased conductivity in the PDDT/PODA blend due to the highly conjugated π-system of PDDT backbone was observed in the presence of nonelectroactive PODA. A red-shift of absorption maximum of PDDT/PODA blend observed in solid state at room temperature. From the FTIR spectra, the gauche-trans conformational structure change of methylene units was investigated in two alkylated polymer blends. The increase of combined heat of fusion of the alkyl side chain melting of PDDT and the endothermic peak of PODA, as well as the interlayer d-spacing of PDDT main chain were also observed with the addition of PODA in blends. A more ordered conformational structure of rigid rod backbone of PDDT was induced due to the attractive intermolecular interaction which can cause cocrystallization between the alkylated side chains of two polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35:1025-1041, 1997
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  • 32
    ISSN: 0887-6266
    Keywords: syndiotactic polystyrene ; polymorphism ; degree of crystallinity ; FTIR spectroscopy ; WAXS characterization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared (FTIR) spectra of syndiotactic polystyrene (s-PS) semicrystalline samples have been examined by using the spectral subtraction approach. For the crystalline forms including trans-planar chains (trigonal α and orthorhombic β) a number of conformational and structural order effects, not previously described in the literature, have been identified. A method based on the results of the spectral subtraction analysis has been developed for the determination of the crystallinity degree and compared with the standard method based on the wide-angle X-ray diffraction patterns. The spectral subtraction analysis on FTIR spectra allows also an easy evaluation of the amount of α and β crystalline phases (often simultaneously present in melt-crystallized samples) although both contain chains in a same conformation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1055-1066, 1997
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  • 33
    ISSN: 0887-6266
    Keywords: thermodynamic interaction ; Flory-Huggins parameter ; rubbery polymer ; gas ; Henry's law coefficient ; partial molar volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Flory-Huggins interaction parameters χ for 23 gases (He, Ne, Ar, Kr, Xe, H2, N2, O2, N2O, CO2, CH4, C2H4, C2H6, C3H6, C3H8, 1,3-C4H6, four C4H8's, n-C4H10, iso-C4H10, and n-C5H12) in five rubbery polymers (1,2-polybutadiene (PB), poly(ethylene-co-vinyl acetate)) (EVAc), polyethylene (PE), polypropylene (PP), and poly(dimethyl siloxane) (PDMS) were determined from either literature data on Henry's law coefficient and partial molar volume or those on sorptive dilation for each polymer/gas system. Values of χ for the gases increased in the order of PDMS 〈 PP ≡ PB 〈 EVAc ≡ PE. Among the gases except He and H2 whose χ values are not reliable, Ne and Xe have respectively the highest and the lowest values of χ for the polyolefins. The χ values of the hydrocarbons were compared together with previously reported χ values of n-alkanes C3-C10. The dependencies of χ upon concentration and temperature were discussed on the basis of the literature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1049-1053, 1997
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  • 34
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: diffusion ; gold, silver ; polycarbonate ; glassy state ; free-volume theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients between 5 × 10-14 and 1 × 10-16 cm2 s-1 have been measured for diffusion of gold and silver in the glassy state of bisphenol trimethylcyclohexanen polycarbonate in the temperature range between Tg = 507 K and 420 K using the radiotracer technique in combination with ion-beam sputtering for serial sectioning. The Arrhenius plot exhibits a downward curvature, which is interpreted within an extension of the free-volume theory to the glassy state by Vrentas and Duda. The very small metal diffusivities in comparison to values for gas molecules of comparable size suggest substantial interaction energies. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35:1043-1048, 1997
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  • 35
    ISSN: 0887-6266
    Keywords: transmission electron microscopy ; block copolymer ; polyimide ; nanofoam ; porous films ; polymer foam ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transmission electron microscopy was performed on a polymeric nanofoam material, derived from a triblock copolymer composed of a fluorinated polyimide center block, 3F/PMDA (derived from pyromelletic dianhydride (PMDA) and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (3F)) and polypropylene oxide (PO) end blocks. The cast and imidized polymer exhibits a microphase-separated morphology consisting of PO microdomains within a polyimide matrix. The final nanofoam material is obtained by decomposing PO microdomains into low molecular weight products, which diffuse out of the polyimide matrix leaving nanometer length scale voids. Ruthenium tetroxide staining prior to microscopy was used to enhance the contrast between the 3F/PMDA matrix and the PO microdomains or voids, which permitted a more detailed view of the microstructure of both the foamed and unfoamed materials. From the power spectra of the micrographs, spatial correlation between the PO microdomains in the unfoamed material and between the voids in the foam were found. An interdomain separation distance of ca. 37 nm was observed. Analysis of the image yielded an average area of 411 nm2 for the PO domains. The analysis indicated that the PO domains were oblong, having average major and minor dimensions of 35 and 12.5 nm, respectively. An autocorrelation of the image showed that the domain center of masses were positioned 41 nm apart, in close agreement with the domain spacing (ca. 37 nm) found as described above. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1067-1076, 1997
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  • 36
    ISSN: 0887-6266
    Keywords: NMR ; dynamics ; polyethylene oxide (PEO) ; polymethyl methacrylate (PMMA) ; polymer blend ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Longitudinal relaxation of proton magnetisation was used to characterize the molecular motions of PEO chains in compatible PEO (hydrogenated)/PMMA (deuterated) blends. Both the temperature and the PEO concentration, Φ, were varied. A maximum in the spin-lattice relaxation rate was observed and its properties were analyzed as a function of Φ. For Φ ≤ 0.50, the maximum is observed below the glass transition temperature of the blend; this shows that PEO chains dispersed in a matrix of PMMA remain highly mobile on a local scale even below Tg(Φ). A frequency-temperature correspondence procedure, applied to the measurements performed at two Larmor frequencies, 32 and 60 MHz, leads to a characteristic correlation time for PEO molecular motions. Its temperature dependence obeys a WLF free volume relation above the glass transition of the blends. The PEO free volume fraction and its thermal expansion are strongly reduced by the presence of the PMMA chains. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1095-1105, 1997
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  • 37
    ISSN: 0887-6266
    Keywords: nucleation ; crystallization kinetics ; polypropylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nucleation rate function is proposed for use in analyzing the overall crystallization kinetics of polymers. This function allows for the possibility that the nucleation rate varies substantially during the crystallization. This feature is particularly useful in analyzing nonisothermal crystallization, but it can be used to analyze isothermal crystallization as well. The nucleation rate function was used in the derivation of a modified transformation kinetics equation of the Avrami type. The modified Avrami equation was found to be suitable for kinetics analysis for the data obtained from nonisothermal crystallization at rapid cooling rates. Kinetics parameters used to describe nonisothermal crystallization under rapid cooling rates are presented and discussed. These include crystallization induction time, plateau (crystallization) temperature, crystallization half-time, crystallization rate constant, Avrami index, and newly defined quantities called nucleation index, geometric index, and nucleation rate constant. The procedure used to obtain the nucleation rate constant and nucleation index for the nucleation rate function is described and illustrated by application to the analysis of the crystallization kinetics of polypropylene. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1077-1093, 1997
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  • 38
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    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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  • 39
    ISSN: 0887-6266
    Keywords: Raman spectra ; longitudinal acoustic mode ; poly(ethylene oxide) ; isothermal crystallization ; noninteger fold ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman longitudinal acoustic mode (LAM) spectra have been obtained during isothermal crystallization from the melt at various temperatures of a poly(ethylene oxide) (PEO) fraction of molecular weight about 3000 and an α,ω-methoxylated fraction (MPEO) derived from it. For both fractions, we find that noninteger fold (NIF) chains are formed in the initial stages of crystallization. With time, and more rapidly at higher crystallization temperatures, the NIF chains transform into integer-fold (IF) structures. The final morphologies of the two fractions are similar, consisting of IF mixed-crystal lamellae composed mainly of extended (E) chains with embedded once-folded (F2) chains. This solid-state transformation from the NIF state may proceed through the F2 state. The effect of hydrogen bonds in the case of PEO is not to change the transformation process but to slow it when compared to MPEO. Comparison with small-angle x-ray scattering (SAXS) data indicates that in both cases the NIF chains are tilted to the lamellar surface and that the tilt from perpendicular eventually disappears as IF chains form at the later stages of crystallization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1117-1126, 1997
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  • 40
    ISSN: 0887-6266
    Keywords: blends ; poly(propylene)s ; phase behavior ; stereoregularity ; solubility parameters ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt miscibility of atactic poly(propylene) (a-PP) with isotactic (i-PP) and syndiotactic poly(propylene) (s-PP), respectively, is investigated by diffusion experiments of i-PP/a-PP/i-PP or s-PP/a-PP/s-PP sandwich specimens using polarized light microscopy. It is shown that the system a-PP/i-PP is miscible in the melt, whereas for the system a-PP/s-PP no evidence for melt mixing is found. Pressure-volume-temperature (PVT) measurements of the three poly(propylene)s are carried out in order to determine the characteristic parameters of the Flory-Orwoll-Vrij equation-of-state theory. Theoretical predictions using the solubility parameter concept are in agreement with the observed miscibility behavior of the blends. Differences in the cohesive energy densities of a-PP and i-PP on the one side, and s-PP on the other side, are found to be responsible for the phase behavior of the mixtures of poly(propylene)s with different stereoregularity. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1135-1144, 1997
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  • 41
    ISSN: 0887-6266
    Keywords: polyetherethersulfone ; sulfonation ; nitrogen and water vapor permeation ; gas drying membranes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The novel polyetherethersulfone (PES-C) prepared from phenol-phthalein in our institute is an amorphous, rigid, tough material with good mechanical properties over a wide temperature range. To improve its water vapor permeability for the application of gas drying, the PES-C was sulfonated with concentrated sulfuric acid and transferred in sodium, cupric, and ferric salt forms. The sulfonation degree can be regulated by controlling the temperature and reaction time. Characterization of sulfonated PES-C in sodium form was made by IR. Some properties of the sulfonated PES-C, such as solubility, glass transition temperature, thermal stability, mechanical properties, and transport properties to nitrogen and water vapor have also been discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2133-2140, 1997
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  • 42
    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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  • 43
    ISSN: 0887-6266
    Keywords: cure kinetics ; diffusion control ; free volume theory ; TGDDM epoxy ; polycarbonate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction kinetics with diffusion control mechanisms are investigated to model the later-stage cure progressing in a co-cured epoxy network that was formed by blending and heating bisphenol-A polycarbonate (PC) with tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM), which together were cured with an aromatic amine hardener. Our earlier studies have demonstrated that the epoxy reacts not only with the amine hardener but also with the PC polymer to eventually form a homogeneous network, and that the initial polymerization and cure for this system can be described by an n-th order kinetics. Using the free volume theory, the effect of diffusion control on the kinetics in the gel/vitrified regimes has been modeled successfully, and a more precise kinetic description for the PC/TGDDM/DDS network systems in the full cure range is resulted. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2141-2150, 1997
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  • 44
    ISSN: 0887-6266
    Keywords: ethylene/butene copolymer ; tensile deformation ; volume change ; mechanical relaxation ; Raman spectroscopy ; mesomorphic phase ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This article deals with the characterization of the structural changes induced by uniaxial extension in the amorphous phase of an ethylene/butene copolymer. Volume change measurements indicate a reversible densification relevant to a strain-induced organization in the amorphous phase. The dynamic mechanical behavior shows an improvement of the β relaxation that reveals an important immobilization of the amorphous chains. The vibrational behavior investigated by means of Raman spectroscopy suggests that the strained amorphous chains are structurally analogous to the mesomorphic interfacial component. A discussion is made about the mechanism of the transformation of the amorphous phase into a mesomorphic structure compared to the more common strain-induced crystallization phenomenon. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2151-2159, 1997
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  • 45
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; ethanol ; n-pentane ; solubility ; diffusivity ; mobility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient of ethanol and of n-pentane in PTMSP, at 27°C, was measured as a function of concentration up to a penetrant content of about 12% by weight, for polymer samples obtained through different processes; differential sorptions and desorptions with vapor phases were considered. In the case of ethanol a nonmonotonous behavior was observed for the diffusivity, while in the case of n-pentane the same property was found to monotonously decrease with increasing the penetrant content. The sorption isotherms were also reported, indicating that n-pentane exhibits a typical dual mode behavior, while ethanol follows an unusual s-shape curve. The chemical potential of the dissolved penetrants, calculated directly from the isotherms, shows the very different importance of the energetic interactions of the two penetrants with the polymer units. In spite of the remarkably different concentration dependencies observed for both solubility and diffusivity of the two penetrants, the mobility factors are in both cases monotonously decreasing with the penetrant concentration, and follow very similar trends. The significant differences observed for the concentration dependence of the diffusion coefficients are, thus, associated to the thermodynamic contributions, which are very different for n-pentane and ethanol. Different polymeric films, obtained through different solvent evaporation processes, show quite different solubility, diffusivity and mobility for both ethanol and n-pentane. On the other hand, the ratio between the mobility of the two penetrants as well as the slope of mobility as function of the concentration remains the same for all the different samples inspected. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2245-2258, 1997
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  • 46
    ISSN: 0887-6266
    Keywords: polyimide membrane ; ultraviolet light irradiation ; crosslinking ; physical changes ; gas permeability ; sorption property ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two types of polyimide membranes; one crosslinkable and the other noncrosslinkable using ultraviolet light irradiation (UV irradiation), were prepared and investigated concerning the effect of UV irradiation on their gas permeabilities and selectivities. Permeability and diffusion coefficients for O2, N2, H2, and CO2 were determined using the vacuum pressure and time lag method. Sorption properties for carbon dioxide were carried out to evaluate the changes in the free volume in the membranes due to the irradiation. In both membranes, permeability coefficients for all gases used in this study decreased and permselectivity, particularly for H2 over N2, increased with increasing UV irradiation time without a significant decrease in the flux of H2. The coefficients depended on the membrane thickness, suggesting asymmetrical changes in both membranes due to UV irradiation. It was suggested by an attenuated total reflection (ATR) FTIR method and analysis of the gas sorption properties of the membranes that the physical changes due to UV irradiation at the irradiated side in both membranes significantly affected their gas permeation properties compared with the chemical changes, especially the crosslinking in the crosslinkable type. © 1997 John Wiley & Sons, Inc. J. Polym Sci B: Polym Phys 35: 2259-2269, 1997
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  • 47
    ISSN: 0887-6266
    Keywords: conformation ; phonon dispersion ; α-helix ; normal modes ; poly(L-leucine) ; density of states ; heat capacity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(L-methionine) (PMet) is one of the two sulfur containing polyamino acids. Raman, FTIR spectra, and heat capacity measurements of PMet have been well interpreted through the normal mode analysis and the density of states derived therefrom. Earlier interpretation of heat capacity data is limited because it is based on the Tarasov model, wherein the concept of group frequency and skeletal similarity are used. A special feature of some dispersion curves is their tendency to bunch in the neighborhood of the helix angle. This has been attributed to the presence of strong intramolecular interactions. Repulsion between the dispersion curves is also observed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2281-2292, 1997
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  • 48
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: conformation transition ; silk fibroin ; chitosan ; blending ; induction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformation of silk fibroin in silk fibroin/chitosan (SF/CS) blend membrane was analyzed by infrared spectrum, X-ray diffractometry, and Raman spectrum. The results demonstrated that the SF could show β-sheet conformation when the SF content in blend membranes was 10% (w/w) and 60-80% (w/w), while the pure SF membrane showed random coil conformation. A mechanism of the conformation transition was suggested in that the SF chain could use the rigid CS chain as a mold plate to stretch itself to form a β-sheet structure according to the strong hydrogen bond between CS and SF. Therefore, a new concept, named “Polymer-Induced Conformation Transition,” was proposed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2293-2296, 1997
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  • 49
    ISSN: 0887-6266
    Keywords: polypropylene ; nitrile rubber ; compatibilization ; dynamic vulcanization ; dynamic mechanical properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of blend ratio and compatibilization on dynamic mechanical properties of PP/NBR blends was investigated at different temperatures. The storage modulus of the blend decreased with increase in rubber content and shows two Tg's indicating the incompatibility of the system. Various composite models have been used to predict the experimental viscoelastic data. The Takayanagi model fit well with the experimental values. The addition of phenolic modified polypropylene (Ph-PP) and maleic modified polypropylene (MA-PP) improved the storage modulus of the blend at lower temperatures. The enhancement in storage modulus was correlated with the change in domain size of dispersed NBR particles. The effect of dynamic vulcanization using sulfur, peroxide, and mixed system on viscoelastic behavior was also studied. Among these peroxide system shows the highest modulus. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2309-2327, 1997
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  • 50
    ISSN: 0887-6266
    Keywords: polyimides ; reflectivity ; moisture absorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Water absorption in thin films (〈1000 Å) of a commercial polyimide was evaluated by monitoring dimensional changes induced by a humid environment. Film thickness was measured using x-ray reflectivity, which is a nondestructive technique offering angstrom resolution in the measurements of thin film or multilayer thickness. The effect of several variables on the absorption of moisture were monitored in polyimide films adhered to polished silicon substrates, including total dry film thickness, exposure time, and the contribution of a coupling agent. The percentage increase in film thickness due to moisture uptake is found to be a weak function of dry film thickness, decreasing as dry film thickness increases, and to be somewhat affected by the use of an interfacial coupling agent. The observed behavior points to the polymer/substrate interface as a strong factor controlling the absorption of moisture in the polyimide/silicon system, and is believed to reflect the presence of a highly moisture-saturated interfacial layer. A bilayer model is proposed, and the feasibility of using this model to describe the observed behavior is considered. Published 1998 John Wiley & Sons, Inc.This article is a US Government work and, as such, is in the public domain in the United States of America. J Polym Sci B: Polym Phys 36: 155-162, 1998
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  • 51
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    Bognor Regis [u.a.] : Wiley-Blackwell
    ISSN: 0887-6266
    Keywords: integral sorption ; rubbery polymers ; moving boundaries ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Simple equations are derived that describe integral sorption and desorption experiments under conditions where moving boundary effects in polymer films and spheres can be large because of high solvent concentrations. General conclusions are formulated about the nature of sorption and desorption experiments for both rectangular and spherical geometries. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 171-180, 1998
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  • 52
    ISSN: 0887-6266
    Keywords: tetramethyl bisphenol-A polyarylate ; aliphatic polyester ; blend ; miscibility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase behavior of blends of tetramethyl bisphenol-A polyarylate (TMPAr) with various linear aliphatic polyesters characterized by the ratio of aliphatic carbons to ester groups in the repeating unit, CH2/COO = 3 ∼ 9, was examined by differential scanning calorimetry and dynamic mechanical analysis. TMPAr/aliphatic polyester blends prepared by solvent casting were found to be miscible when the CH2/COO ratio of aliphatic polyesters was larger than 4 and up to 9. The thermodynamic interaction parameter, B for the miscible blends was determined by the analysis of the depression of the melting point of polyester using the Hoffman-Weeks method. From the analysis of the heat of mixing data using a binary interaction model, it was concluded that strong unfavorable intramolecular interaction exists between the —CH2— and —COO— units in aliphatic polyesters and that four substituted methyl groups produces more favorable effects on the miscibility TMPAr with aliphatic polyesters. © 1998 John Wiley & Sons, Inc. J Polym Sci 36: 201-212, 1998
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  • 53
    ISSN: 0887-6266
    Keywords: entangled polymer solution ; double-step strain rate ; flow birefringence ; tube model ; segmental stretch ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments measuring the orientation angle and birefringence in startup and double-step strain rate flows were conducted on a 3.0 wt % 8.42 × 106 molecular weight polystyrene solution in a Couette flow cell. A phase-modulated flow birefringence apparatus was used to noninvasively probe the sample. Upon startup from rest, the orientation angle undershoots its final steady-state value, as seen by earlier investigators. When the shear rate undergoes a step increase from one nonzero value to another, the amplitude of this undershoot is decreased. However, a more significant effect is a shorter time scale overshoot in the orientation angle that is highly counterintuitive in the sense that an increase of shear rate initially produces a rotation of chain segments away from the flow direction. Similarly, a step decrease in shear rate yields an initial transient rotation toward the flow direction. In both cases, the height of the peaks depends upon the magnitude of the shear rate jump, and the width of the peaks is a function of the final shear rate. The longer time transients in the startup and step increase experiments reflect an apparent change in the relaxation time for segment orientation, which we tentatively attribute to a combination of tube dilation and convective constraint release. The shorter time scale over- and undershoots in the orientation angle appear to be qualitatively explained by considering the differences in extension or contraction of segments along the polymer chain. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 265-280, 1998
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  • 54
    ISSN: 0887-6266
    Keywords: side-chain liquid-crystalline polymer membrane ; pervaporation ; benzene/cyclohexane mixture ; state-transformation ; benzene permselectivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a benzene/cyclohexane mixture of 10 wt % benzene was permeated through side-chain liquid-crystalline polymer (LCP) membranes by pervaporation at various temperatures, the permeation rate increased with increasing permeation temperature. The LCP membranes also exhibited a benzene permselectivity. The permselectivity for the benzene/cyclohexane mixture through the LCP membrane was different in the glassy, liquid-crystalline, and isotropic states. The LCP membrane had different apparent activation energies for permeation at each state. LCP membrane in the liquid-crystalline state had the highest apparent activation energy of the three states. Results suggest that the benzene permselectivity was influenced by changes in the LCP membrane structure, i.e., a state-transformation. It was found that a balance of the orientation of mesogenic groups and the flexibility of the siloxane chains was very important for benzene permselectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 281-288, 1998
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  • 55
    ISSN: 0887-6266
    Keywords: polydimethylsiloxane ; permeability ; sorption ; mixed gas permeation ; clustering ; acetone/nitrogen separation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permeability of polydimethylsiloxane [PDMS] to acetone, nitrogen, and acetone/nitrogen mixtures has been determined at 28°C. In pure gas experiments, the permeability of PDMS to nitrogen was 245 × 10-10 cm3(STP) · cm/cm2 · s · cmHg and was independent of pressure. The permeability of PDMS to acetone vapor increased exponentially with increasing acetone pressure. PDMS is much more permeable to acetone than to nitrogen; acetone/nitrogen selectivity increases from 85 to 185 as acetone partial pressure in the feed increases from 0 to 67% of saturation. In mixed gas permeation experiments, the nitrogen permeability coefficient is independent of acetone relative pressure and is equal to the pure gas permeability coefficient. The acetone permeability coefficient has the same value in both mixed gas and pure acetone permeation experiments. Average acetone diffusivity in PDMS, determined as the ratio of permeability to solubility, decreases with increasing acetone concentration due to mild clustering of acetone in the polymer (because acetone is a poor solvent for PDMS) and changes in the polymer-penetrant thermodynamic interactions which influence diffusion coefficients. A Zimm-Lundberg analysis of the acetone sorption isotherm is also consistent with acetone clustering in PDMS. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 289-301, 1998
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  • 56
    ISSN: 0887-6266
    Keywords: pressure-sensitive adhesive ; PSA ; tackifier ; tack adhesion ; polyisoprene ; poly(ethylene-propylene) ; pulsed gradient spin echo-nuclear magnetic resonance ; PGSE-NMR ; diffusion ; n-butyl ester of abietic acid ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed study of the mobility of a tackifying resin in a pressure-sensitive adhesive (PSA) has been done for the first time. The objective of this work is to relate changes in adhesive performance with tackifier loading to tackifier mobility. Tackifiers are low-molecular weight resins that improve the overall performance of PSAs. They increase the adhesive tack or the ability to form a bond of measurable strength after brief contact under slight applied pressure. In this study the diffusion of n-butyl ester of abietic acid (n-BEAA) in either polyisoprene (PI) (Mw = 195,000 Mw/Mn ∼ 1.05) or poly(ethylene-propylene) (PEP) (Mw = 40,000 Mw/Mn ∼ 2.30) was measured by Pulsed Gradient Spin Echo-Nuclear Magnetic Resonance (PGSE-NMR) as a function of both tackifier concentration and temperature. The concentration dependence of the tackifier's diffusion coefficient was weak for both systems. The weak variation in mobility with composition for the PI/n-BEAA system was consistent with that system's weak variation in tack with composition. On the other hand, blends of PEP/n-BEAA showed only modest variation in mobility, even though these adhesive systems showed appreciable enhancement of tack at intermediate compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 373-381, 1998
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  • 57
    ISSN: 0887-6266
    Keywords: syndiotactic polypropylene ; form-IV ; form II ; kink bands ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The packing of the chains in (T6G2T2G2)n conformation of the form IV of s-PP is revisited on the basis of packing energy and structure factor calculations. According to this analysis, an alternative mode of packing has been suggested. A monoclinic structural model, with the unit cell centered on the C face, is obtained, after small changes of the atomic coordinates in the triclinic structural model as proposed by Chatani et al. The monoclinic model presents a lower packing energy than the triclinic model and a good agreement between the calculated and observed structure factors. The triclinic structural model implies that all the chains are rotated by the same amount around the chain axis with respect to the monoclinic structural model. Since clockwise and counter clockwise rotations are equivalent, the monoclinic structural model may be taken as descriptive of the order in the long range, for the form IV of s-PP, or in other terms, descriptive of an average structure (space group C2, unit cell constants equal to am = 14.17 Å, bm = 5.72 Å, cm = 11.6 Å, and βm = 108.8°). The triclinic structural model for this polymorph, instead (space group P1, unit cell constants equal to at = 5.72 Å, bt = 7.64 Å, ct = 11.60 Å, αt = 73.1°, βt = 88.8°, γt = 112.0°) is probably more properly descriptive of local situation of order (the symmetry, locally, is broken). Analogies between the monoclinic limit ordered structural model for the form IV and the orthorhombic limit ordered structural model for the form II (with chains in the more stable (TTGG)n conformation) of s-PP are also provided. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 395-402, 1998
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  • 58
    ISSN: 0887-6266
    Keywords: ion-selective membranes ; gel crystallization ; poly(siloxanes) ; crown-ethers ; calixarenes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A one-step procedure for the preparation of ion-selective membranes is described. The method employs the thermally induced gel crystallization of ultrahigh molecular weight poly(ethylene) (UHMW-PE) from a dilute xylene solution. After evaporation of the xylene, a microporous UHMW-PE film remains, which can serve as the support for liquid and polymeric ion-selective membranes. The addition of a membrane solvent and suitable receptor molecules to the xylene solution allows a one-step incorporation of these membrane components into the UHMW-PE support. The influence of the preparation conditions of the UHMW-PE support on the rates of the p-tert-butylcalix[4]arene tetraethylester-mediated transport of NaClO4 was studied. Two concepts to improve the life-time of the membranes are introduced. In a first approach, the addition of photocrosslinkable nitril-substituted siloxane copolymers to the membrane phase has been evaluated. The enhanced viscosity of the membrane phase reduces leaching of carrier and solvent molecules from the membrane into the aqueous phases. In a second approach, the solvent is omitted and the membrane-phase merely consists of a benzo-15-crown-5 or calix[4]arene modified siloxane-copolymer, which is substituted to such a degree that ion transport no longer has to take place via diffusion of host-guest complexes but by jumping of the cations from one fixed carrier to a neighboring carrier. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 383-394, 1998