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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1217-1226 
    ISSN: 0887-624X
    Keywords: polypropylene ; pyrene ; two-solute system ; pulse radiolysis ; solute ionic species ; solute excited states ; low-temperature radiolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A pulse radiolysis study of isotactic polypropylene (PP) film has been carried out with the main aims of investigating charge trapping in an undoped system and solute radical ion generation in an pyrene (Py) doped matrix. In PP, pulse radiolysis gives electron-positive hole pairs. The electron can be stabilized in the undoped system as a trapped electron, et-. The transient absorption spectrum of et- in the near-IR (up to 1800 nm) was observed in the temperature range 30-100 K. This IR absorption was not detected in the case of oxidized PP. In such a matrix electrons can be scavenged by oxidation products generating respective radical-anions (absorption in the UV RANGE, λ 〈 350 nm). In a doped matrix transient absorption bands centered at 450 and 500 nm were observed which can be assigned to the Py radical cation and anion, respectively. The recombination of these ionic species leads to monomer excited-state formation observed during and after the 17 ns pulse. Contrary to the Py-doped polyethylene no excimer emission was detected at room temperature even if Py content in PP was close to 0.02 mol dm-3. The rate of Py radical-ion decay was found to be temperature dependent. Two linear parts of the Arrhenius plot were observed which intersected at ca. 240 K, the glass transition temperature, Tg, for PP. The activation energies calculated for two parts of Arrhenius plot were equal to 111 and ca. 0.78 kJ mol-1 for T 〉 Tg and T 〈 Tg, respectively. Some preliminary results concerning the ionic processes in PP containing two solutes (Py, 3,3′-dimethyldiphenyl) were presented. The mechanism of ionic recombination in PP will be proposed and discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1217-1226, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 299-305 
    ISSN: 0887-624X
    Keywords: poly(methylmethacrylate) ; pulse radiolysis ; charge scavenging ; doped polymers ; excited states ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectra of transients produced in pulse-irradiated pure poly(methyl methacrylate), PMMA, at room and ∼ 130 K temperatures were measured. The intermediates were identified as PMMA radicals and radical anions. In the pulse-irradiated PMMA-pyrene (Py) system the solute excited states and radical ions were produced. Scavenging of negative charges by Py was directly observed at 130 K in a µs time scale. Py fluorescence was found to be produced mainly as a result of Čerenkov photoexcitation. At room temperature, some contribution of ionic mechanism to Py fluorescence formation was found. © 1997 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1209-1215 
    ISSN: 0887-624X
    Keywords: poly(methyl methacrylate) ; pyrene ; pulse radiolysis ; radical ion decay ; ion recombination ; fluorescence ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A pulse radiolysis study of poly(methyl methacrylate) in the presence of pyrene has been carried out in the temperature range 100-295 K. The concentration of pyrene was changed from 10-3 to 10-1 mol dm-3. The absorption/emission spectra and kinetics of solute excited states and solute radical ions were investigated. It was found that pyrene excited states were formed as a result of their radical ion recombination in a time scale up to seconds. The decay of solute radical ions was influenced by photobleaching and can be described by a time-dependent rate constant. The activation energy of Py ions decay was temperature dependent and was equal to 35.7 and 1.2 kJ/mol for temperatures 〉Tγ and 〈Tγ, respectively, where Tγ ∼ 175 K represented the transition temperature responsible for γ-relaxation. The reaction mechanism was proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1209-1215, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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