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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 689-708 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using laser interferometry, we have determined in situ the thickness increase with time of thin supported polyimide films (4-8 μm in initial thickness) immersed in n-methyl-2-pyrrolidone (NMP) as a function of NMP temperature (22-120°C). Similar experiments were also performed in dimethyl sulfoxide (DMSO) at 22°C with polyimide films of 4.1 μm in thickness. For NMP, the equilibrium fractional thickness increase (about 20%) is independent of initial polyimide thickness and temperature. The time scale for reaching equilibrium sharply decreases with temperature from 2-3 days at 22°C to 30-60 min at 120°C. Compared with NMP, the rate of DMSO sorption is considerably faster, reaching equilibrium swelling of about 28% in about 5 h at 22°C. To describe the transport process, we applied a phenomenological model proposed by Astarita and Sarti1 but reformulated in polymer fixed frame to enable straightforward comparison with the thickness data. Our analysis indicated that the transport of NMP is best described as anomalous, that is, intermediate between diffusion controlled and case II transport. The effective diffusion coefficient Deff and the front velocity U0 at 22°C were found to be 3-6 × 10-12 cm2/s and 8 × 10-9 cm/s, respectively. Our front velocity is in good accord with the value of 6 × 10-9 cm/s obtained for a similar polyimide based on gravimetric measurements.2 Both Deff and U0 show an activation energy of ∼56 kJ/mol. For DMSO, however, the transport is clearly case II. The front velocity at 22°C was found to be about 6 × 10-8 cm/s, which is about four times that obtained by Rutherford back-scattering spectrometry.3
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 38 (1989), S. 937-950 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A bending-beam technique has been employed to study the effects of film thickness (7-55 μm) and rate of cooling during film preparation (∼ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (˜ 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7-13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2-4 × 10-9 cm2/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ˜ 108 dyn/cm2) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (∼ 2 × 10-8 cm2/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 43 (1991), S. 709-721 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Solvent transport in multilayer thin film structures can induce damaging stresses. It is important to understand these quantitatively for the design of processing methods for microelectronics manufacture. As a model for such systems, this article focuses on the connection between solvent transport in a thin, supported film and the induced bending curvature of the film/substrate combination. We develop a simple mechanical model to calculate the bending curvature based on the transport-induced stresses. A phenomenological moving boundary description of non-Fickian solvent transport often found in glassy polymers has been used. The evaluation of dimensionless bending curvature for a number of generic cases is presented. As an application of the model, experimental data for a polymide (PI)/quartz-n-methyl-2-pyrrolidinone (NMP) system involving significant swelling (15-20%) of the PI film is analyzed. The analysis shows that the measured bending during the transport of NMP in the PI film compares well with that predicted based on an “intermediate,” non-Fickian diffusion mechanism of NMP, consistent with the finding obtained from a laser interferometric study. Estimation of the swelling-induced stress shows that it is large and as significant as that due to thermal “curing.”
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 27 (1989), S. 235-237 
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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