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Volumn 29, Issue 11, 1996, Pages 3898-3908

Small molecule probe diffusion in thin polymer films near the glass transition: A novel approach using fluorescence nonradiative energy transfer

Author keywords

[No Author keywords available]

Indexed keywords

ANNEALING; DIFFUSION IN SOLIDS; DOPING (ADDITIVES); ENERGY TRANSFER; FLUORESCENCE; GLASS TRANSITION; MOLECULAR DYNAMICS; ORGANIC POLYMERS; RELAXATION PROCESSES; THERMAL EFFECTS;

EID: 0030143462     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma960024j     Document Type: Article
Times cited : (91)

References (100)
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    • Rutherford backscattering spectroscopy has been employed recently to follow the non-Fickian diffusion of resorcinol bis(diphenyl phosphate) in glassy Ultem, a poly(ether imide) (Nealey, P. F.; Cohen, R. E.; Argon, A. S. Polymer 1995, 36, 3687). Magnetic resonance imaging has also been used to monitor Fickian and non-Fickian diffusion of sorbents in polymers (Ercken, M.; Adriaensens, D.; Vanderzande, D.; Gelan, J. Macromolecules 1995, 28, 8541).
    • (1995) Polymer , vol.36 , pp. 3687
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    • Rutherford backscattering spectroscopy has been employed recently to follow the non-Fickian diffusion of resorcinol bis(diphenyl phosphate) in glassy Ultem, a poly(ether imide) (Nealey, P. F.; Cohen, R. E.; Argon, A. S. Polymer 1995, 36, 3687). Magnetic resonance imaging has also been used to monitor Fickian and non-Fickian diffusion of sorbents in polymers (Ercken, M.; Adriaensens, D.; Vanderzande, D.; Gelan, J. Macromolecules 1995, 28, 8541).
    • (1995) Macromolecules , vol.28 , pp. 8541
    • Ercken, M.1    Adriaensens, D.2    Vanderzande, D.3    Gelan, J.4
  • 38
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    • note
    • g's as measured by DSC for the polymers employed in this study, PiBMA and PEMA, were unchanged by the low level of labeling or doping with chromophores; therefore, the introduction of the fluorescent chromophores at low levels does not significantly affect polymer dynamics in these systems. Thus, the dopant chromophores can be considered as diffusing from one film, of infinitesimal chromophore content, to another of zero concentration. Consequently, it can be assumed that the layered films used in this study constitute a continuous matrix through which the donor molecules diffuse.
  • 41
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    • Butterworths Scientific Publications: London
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    • note
    • -5, which is negligible.
  • 43
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    • note
    • o is 3.5 nm, this interfacial region constitutes at most a fraction of a percent of the total "sandwich" thickness. Consequently, even in the worst case studied here, <1% of the chromophores in the film sandwich are close enough before annealing to undergo any NRET.
  • 45
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    • Manuscript in preparation
    • g even upon the addition of several weight percent of a variety of dopants. See ref 2c and Hamilton, K. E.; Torkelson, J. M. Manuscript in preparation.
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    • note
    • -5 M. Solutions used to prepare decaryclene-doped films for this study were sufficiently dilute to prevent aggregate formation.
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  • 53
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    • 2/s), these differences are potentially resolvable only in the case of very large Förster radii (6 nm) and very thin films (65 nm was the example used) at very short diffusion times (<10 min). Such effects not resolvable within experimental error for any of the conditions employed in this study, justifying the comparison of experimental data to the prediction of the Förster theory.
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    • note
    • Although pyrene-labeled polymer films produce non-single-exponential decay profiles, polymer films containing pyrene as a dopant chromophore do, in fact, yield single-exponential decay profiles. Single-exponential decays with a pyrene dopant excited-state lifetime of 291 ns have been obtained at room temperature from glassy PiBMA fibns as thin as 2 μm containing as little as 0.05 mol % pyrene.
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    • Dhinojwala, A. Ph.D. Thesis, Northwestern University, Evanston, IL, 1994.
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    • note
    • g/T) can be neglected with little error (this is true even if the Stokes-Einstein equation is not strictly applicable as the parameter ξ accounts for the deviation from Stokes-Einstein behavior; (see references 3 and 15 where this has been done previously).
  • 67
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    • note
    • 2g, are able to fit the diffusion data with somewhat different ξ values, too much emphasis should not be placed on the exact calculated values of ξ. For example, for the diffusion of TTI in polystyrene, ref 3 lists a ξ value of 0.75, whereas ref 18 cites that ξ = 0.84; it may be stated that in this case ξ ≈ 0.8. In addition the value of ξ = 1.06 for TTI in polyisoprene reported in ref 18 could be considered to be 1.00, within experimental error. In the present study, it may be sufficient to note that ξ is about 0.4 for pyrene in PiBMA and about 0.8-0.9 for decacyclene in PiBMA.
  • 81
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    • note
    • (c) Note that in the studies listed in parts a and b, probe rotational reorientation measurements were made in polystyrene and compared to translational diffusion results from similarly sized, but not identical, probes in polystyrene as reported in ref 3.
  • 98
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    • manuscript submitted
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    • note
    • g in methacrylate-based polymers.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.