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  • International Union of Crystallography  (1)
  • Wiley-Blackwell  (1)
  • 1
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: This paper presents the application of static time-of-flight secondary ion mass spectrometry (ToF-SIMS) to the analysis of polymeric materials, including chemically modified polymers and polymer additives. Throuh the detection of intact functionalized oligomers, analysis of poly(styrene) functionalized with perfluoroalkyl chlorosilane provides confirmation of a successful endgroup termination for a living polymerization. The calculated molecular weight distribution also is in good agreement with chromatrographic results. High mass resolution studies allow monitoring of the hydrogenation of a poly(butadiene) polymer through increases in oligomer mass due to proton addition. The quantitative ToF-SIMS results for the extent of hydrogenation for a specific oligomer are lower than the values averaged over all oligomers as determined by magnetic resonance. The usefulness of ToF-SIMS for determination of trace-level polymer additives is demonstrated for linear low-density poly(ethylene) (LLDPE). Application of a 150 nm thick evaporated Ag pattern enables in situ detection of the five trace additives present in the LLDPE matrix, and also provides information on additive surface migration and surface oxidation. A study of the silver cationization process for the silver-patterned LLDPE surface suggests differences in diffusion and/or ionization processes for two additives. This is confirmed with mass-resolved ion imaging to show the lateral distribution of the silver-cationized signals for various polymer additive molecular ions. Finally, poly(styrene) (Mn = 1300) coated with a continuous silver overlayer is investigated. The ToF-SIMS-determined molecular weight distribution shifts to lower masses, suggesting the greater diffusion of shorter polymer chains through the silver overlayer.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 1997-10-01
    Description: Above its critical point, carbon dioxide forms a super-critical fluid, which promises to be an environmentally responsible replacement for the organic solvents traditionally used in polymerizations. Many lipophilic polymers such as polystyrene (PS) are insoluble in CO2, though polymerizations may be accomplished via the use of PS-fluoropolymer stabilizers, which act as emulsifying agents. Small-angle neutron and X-ray scattering have been used to show that these molecules form micelles with a CO2-phobic PS core and a CO2-philic fluoropolymer corona. When the PS block was fixed in length and the fluorinated corona block was varied, the number of block copolymer molecules per micelle (six to seven) remained constant. Thus, the coronal block molecular weight exerts negligible influence on the aggregation number, in accordance with the theoretical predictions of Halperin, Tirrell & Lodge [Adv. Polym. Sci. (1992), 100, 31–46]. These observations are relevant to understanding the mechanisms of micellization and solubilization in supercritical fluids.
    Print ISSN: 0021-8898
    Electronic ISSN: 1600-5767
    Topics: Geosciences , Physics
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