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  • General Chemistry  (168)
  • Physics  (46)
  • Atomic, Molecular and Optical Physics  (28)
  • Wiley-Blackwell  (242)
  • National Academy of Sciences
  • 1995-1999  (242)
  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2597-2605 
    ISSN: 0887-6266
    Keywords: positron annihilation ; open space ; relaxation ; subsurface ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Open spaces in the subsurface region (〈10 μm) of very low density polyethylene were probed by a monoenergetic positron beam. From measurements of Doppler broadening spectra measurements of the annihilation radiation and the lifetime spectra of positrons as a function of incident positron energy, the size of the open spaces in the region of 0-3 μm was found to be larger than that in the deeper region. This was attributed to the cooperative motion of large segments of molecules which is activated near the surface. After the freezing in of such motions (below 230 K), although the lineshape parameter S in the bulk was almost constant, S in the region of 0-3 μm decreased with decreasing temperature. This discrepancy was associated with the presence of the open spaces with an excess content and the resultant contraction of amorphous structure near the surface. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2597-2605, 1998
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0947-6539
    Keywords: exchange coupling ; ferromagnetic properties ; ligand design ; magnetic properties ; multimetallic complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An approach is suggested for using ligands to control exchange coupling in multinuclear ions. The idea arose from structural, EPR, and magnetic studies of [PPh4]3 (Scheme 1). Ferromagnetic coupling has been found between the CoII and each CoIII in 3 with J = -22 ± 5 cm-1 (JS1 · S2). It is suggested that dominant antiferromagnetic superexchange is absent because of the strong σ-donor capacity of the tetradentate ligand [k4-PAC*]4- (Fig. 1). The ligand interacts at CoIII primarily with a single d orbital; it is thus best able to participate in superexchange. The interaction makes the unique d orbital strongly σ-antibonding and empty for each d6, S = 1, CoIII ion in 3, that is, unavailable for antiferromagnetic coupling, but available for ferromagnetic pathways by a Goodenough-Kanamori mechanism. By corollary, when any [k4-PAC*]4--type ligand with any magnetic ion Ma in the tetradentate site binds any magnetic ion Mb in the bidentate site, ferromagnetic coupling should be favored provided Ma is not a d9 ion.
    Additional Material: 12 Ill.
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  • 3
    ISSN: 0947-6539
    Keywords: crown ethers ; dialkylammonium salts ; hydrogen bonding ; molecular recognition ; pseudorotaxanes ; self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A very simple self-assembling system, which produces inclusion complexes with pseudorotaxane geometries, is described. The self-assembly of eight pseudorotaxanes with a range of stoichiometries-1:1, 1:2, 2:1, and 2:2 (host:guest)-has been achieved. These pseudorotaxanes self-assemble from readily available components-well-known crown ethers, such as dibenzo[24]crown-8 and bis-p-phenylene[34]crown-10, and secondary dialkylammonium hexafluorophosphate salts, such as (PhCH2)2NH+2PF-6 and (nBu)2NH+2PF-6-and have been characterized not only in the solid state, but also in solution and in the “gas phase”. The pseudorotaxanes are stabilized largely by hydrogen-bonding interactions and, in some instances, by aryl-aryl interactions.
    Additional Material: 40 Ill.
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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. 281-288 
    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
    Additional Material: 7 Ill.
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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. 1857-1872 
    ISSN: 0887-6266
    Keywords: hybrid polymers ; rheology ; reptation ; silsesquioxane polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report on the viscoelastic behavior of linear thermoplastic nonpolar hybrid inorganic-organic polymers. These materials have been synthesized through copolymerization of an oligomeric inorganic macromer with 4-methylstyrene where the inorganic portion of the material is a well-defined polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(CH2CH2C6H4C=CH2), with R = c-C6H11 or c-C5H9. A series of 4-methyl styrene copolymers with approximately 4, 8, and 16 mol % POSS macromer incorporation were investigated. Rheological measurements show that the polymer dynamics are profoundly affected as the percent of POSS increases. In particular, a high-temperature rubbery plateau develops (where a terminal zone is not observed), despite the fact that the parent poly 4-methylstyrene is unentangled. It is also observed that the thermal properties are influenced as the percent of POSS incorporation increases, with increases in the glass and decomposition temperatures. The results suggest that interchain interactions between the massive inorganic groups are responsible for the retardation of polymer chain motion, a mechanism similar to the “sticky reptation” model conceived for hydrogen-bonded elastomers and developed by Leibler et al. [Macromolecules, 24, 4701 (1991)]. Control over the interchain interactions would also give rise to the observed increases in glass transition and the establishment of a rubbery plateau. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1857-1872, 1998
    Additional Material: 14 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    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
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 699-707 
    ISSN: 0887-6266
    Keywords: side-chain liquid-crystalline polymer ; pervaporation ; benzene/cyclohexane mixtures ; state transformation ; permselectivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The side-chain liquid-crystalline polymer (LCP) was synthesized by the addition of the mesogenic monomer to poly(methylsiloxane) with Pt catalyst. When the benzene/cyclohexane mixtures were permeated through the LCP membranes by pervaporation at various temperatures, the permeation rate increased with increasing benzene concentration in the feed solution and permeation temperature. Though the LCP membranes exhibited a benzene permselectivity, a mechanism of the permeation and separation for the benzene/cyclohexane mixtures was different in the glassy, liquid-crystalline and isotropic state of the LCP membranes. These results suggested that the permselectivity was fairly influenced by the change of the LCP membrane structure, that is, a state transformation. It was found that a balance of the orientation of mesogenic groups and flexibility of siloxane chains is very important for the permeability and selectivity. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 699-707, 1997
    Additional Material: 5 Ill.
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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. 2781-2792 
    ISSN: 0887-6266
    Keywords: waterborne epoxy ; surfactant ; cooperativity ; Fox equation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have investigated epoxies based on the diglycidyl ether of bisphenol A (DGEBA) cured with 2-ethyl-4-methylimidazole (EMI-24) in the presence of the nonionic surfactant Triton X-100. A goal was to determine if the viscoelastic properties of the epoxy-surfactant system differed when prepared in bulk form, as opposed to being cast as a thin film on the surface of E-glass cloth. Such a combination of materials has generated great interest for potential use in the construction of laminated circuit boards. Using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and atomic force microscopy (AFM), it was determined that the surfactant acts as a plasticizer and is miscible with the epoxy system in concentrations up to 15% by weight. The glass transition temperature (Tg) depression of the epoxy due to the surfactant was accurately described by the Fox equation. DMA master curves were constructed in the frequency domain. The temperature dependence of the shift factors was used to determine the fragility of each of the samples studied. It was found that the fragility (cooperativity) of the epoxy decreased as the concentration of surfactant increased, presumably due to a reduction of intermolecular constraints. The fragility of the combined epoxy-surfactant system increased when cast on the surface of the E-glass cloth. Results for our model epoxy-surfactant resin were in excellent agreement with those obtained using a commercially available aqueous waterborne epoxy resin. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2781-2792, 1998
    Additional Material: 12 Ill.
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  • 9
    ISSN: 0044-8249
    Keywords: Käfigverbindungen ; Selbstorganisation ; Supramolekulare Chemie ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 10
    ISSN: 0044-8249
    Keywords: Anionenkomplexierung ; Nichtkovalente Wechselwirkungen ; Selbstorganisation ; Supramolekulare Chemie ; Wirt-Gast-Chemie ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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