Translational diffusion in polydisperse polymer samples studied by dynamic imaging of diffusion ESR

Journal of Physical Chemistry

Volumn 100, Issue 39, 1996, Pages 15856-15866

  Xu, Dajiang ^a   Hall, Elizabeth ^b   Ober, Christopher K ^c   Moscicki, Jozef K ^d   Freed, Jack H ^a  

^a Department of Obstetrics Gynecology   (United States)

^b LUCENT TECHNOLOGIES   (United States)

^c Cornell University   (United States)

^d JAGIELLONIAN UNIVERSITY   (Poland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000545928     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp960513l     Document Type: Article

References (29)

1. Moscicki, J. K.; Shin, Y.-K.; Freed, J. H. In EPR Imaging and In Vivo EPR; Eaton, G. F., Eaton, S. S., Ohno, K., Eds.; CRC Press: Boca Raton, 1991; Chapter 19.
2. Moscicki, J. K.; Shin, Y.-K.; Freed, J. H. (a) J. Magn. Reson. 1989, 84, 554;
3. (b) J. Chem. Phys. 1993, 99, 634.
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6. Freed, J. H.; Nayeem, A.; Rananavare, S. B. In The Molecular Dynamics of Liquid Crystals; Luckhurst, G. R., Veracini, C. A., Eds.; Kluwer: Netherlands, 1994; Chapter 12.
7. (a) Doi, M.; Edwards, S. F. The Theory of Polymer Dynamics; Clarendon Press: Oxford, New York, 1986.
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10. Schlick and co-workers [Schlick, S.; Pilar, J.; Kweon, S.-C.; Vacik, J.; Gao, Z.; Labsky, J. Macromolecules 1995, 28, 5780] have employed spectral-spatial ESR imaging to study diffusion of small molecular weight molecules in polymers. Theirs is a case of monodisperse diffusion.
11. A preliminary account of this work was presented at the ACS meeting March, 1994, San Diego [Xu, D.; Budil, D. E.; Freed, J. H.; Hall, E.; Ober, C. K. Polym. Prepr. 1994, 35, 809]. It did not consider the polydispersity of the polymer samples.
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20. We attempted to confirm these measured S values with X-ray diffraction measurements of the solid samples, which showed weakly orientational dependent ESR spectra at room temperature. Station camera experiments using a Cu Kα source and flat film exposed for 8 h failed to show any discernible alignment. We believe this may be due to the lower sensitivity of the X-ray technique or perhaps to a partial loss of order during crystallization after the DID-ESR experiment.
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28. 23 simply includes the geometric factors appropriate when observations are made on partially aligned liquid crystalline systems. It does not allow for the possibility that the degree of macroscopic alignment has an effect on the microscopic structure, hence on the diffusion process.
29. 0, α, and β. Then an analysis of the diffusional polydispersity in commercial samples could be used to obtain their molecular weight distributions.