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A High-Field EPR Study of the Accelerated Dynamics of the Amorphous Fraction of Semicrystalline Poly(dimethylsiloxane) at the Melting Point

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Abstract

The reorientation of a small paramagnetic tracer in poly(dimethylsiloxane) (PDMS) has been investigated by high-field electron paramagnetic resonance spectroscopy at a Larmor frequency of 285 GHz. The tracer is confined in the disordered phase of the semicrystalline PDMS. A sudden change of the rotational dynamics is observed close to the melting point (213 K) of the crystallites. This points to strong coupling between the crystalline and the disordered fractions of PDMS. Below the glass transition (\(T_\mathrm{g} \sim 150 \mathrm{K}\)), the tracer reorientation occurs via small angle jumps, with no apparent distribution of the correlation times. Above \(T_\mathrm{g}\), a power-law distribution of correlation times is evidenced.

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References

  1. U.W. Gedde, Polymer Physics (Chapman and Hall, London, 1995)

    Google Scholar 

  2. M. Cocca, M.L.D. Lorenzo, M. Malinconico, V. Frezza, Eur. Polym. J. 47, 1073 (2011)

    Article  Google Scholar 

  3. M. Drieskens, R. Peeters, J. Mullens, D. Franco, P.J. Lemstra, D.G. Hristova-Bogaerds, J. Polym. Sci. Part B Polym. Phys. 47, 2247 (2009)

  4. S.C. George, S. Thomas, Prog. Polym. Sci. 26, 985 (2001)

    Article  Google Scholar 

  5. L.J. Berliner, J. Reuben (eds.), Biological Magnetic Resonance (Plenum, New York, 1989)

    Google Scholar 

  6. G.G. Cameron, in Comprehensive Polymer Science, ed. by C. Booth, C. Price (Pergamon, Oxford, 1989)

  7. B. Rånby, J. Rabek, ESR Spettroscopy in Polymer Research (Springer, Berlin, 1977)

    Book  Google Scholar 

  8. M. Faetti, M. Giordano, D. Leporini, L. Pardi, Macromolecules 32, 1876 (1999)

    Article  ADS  Google Scholar 

  9. V. Bercu, M. Martinelli, C.A. Massa, L.A. Pardi, D. Leporini, J. Phys. Condens. Matter 16, L479 (2004)

    Article  ADS  Google Scholar 

  10. V. Bercu, M. Martinelli, L. Pardi, C.A. Massa, D. Leporini, Z. Phys. Chemie 226, 1379 (2012)

    Article  Google Scholar 

  11. V. Bercu, M. Martinelli, C.A. Massa, L.A. Pardi, D. Leporini, J. Chem. Phys. 123, 174906 (2005)

    Article  ADS  Google Scholar 

  12. R. Ross, J. Chem. Phys. 42, 3919 (1965)

    Article  ADS  Google Scholar 

  13. J.L. Jr., G. Reed, J. Phys. Chem. 75, 1202 (1971)

  14. M.K. Ahn, J. Chem. Phys. 64, 134 (1976)

    Article  ADS  Google Scholar 

  15. D. Banerjee, S.N. Bhat, S.V. Bhat, D. Leporini, Proc. Natl. Acad. Sci. USA 106, 11448 (2009)

    Article  ADS  Google Scholar 

  16. D. Banerjee, S.N. Bhat, S.V. Bhat, D. Leporini, PLOS One 7, e44382 (2012)

    Article  ADS  Google Scholar 

  17. D. Banerjee, S.V. Bhat, D. Leporini, Adv. Chem. Phys. 152, 1 (2013)

    Google Scholar 

  18. M.M. Dorio, J.C.W. Chien, Macromolecules 8, 734 (1975)

    Article  ADS  Google Scholar 

  19. S. Kutsumizu, M. Goto, S. Yano, Macromolecules 37, 4821 (2004)

    Article  ADS  Google Scholar 

  20. M.S. Jahan, in UHMWPE Biomaterials Handbook, ed. by S.M. Kurtz (Academic Press, London, 2009), pp. 433–450

  21. K. Makuuchi, S. Cheng, Radiation Processing of Polymer Materials and Its Industrial Applications (Wiley, Hoboken, 2012)

    Book  Google Scholar 

  22. J.W. Saalmueller, H.W. Long, T. Volkmer, U. Wiesner, G.G. Maresch, H.W. Spiess, J. Polym. Sci. Pt. B-Polym. Phys. 34(6), 1093 (1996)

    Article  ADS  Google Scholar 

  23. R. Lund, A. Alegría, L. Goitandía, J. Colmenero, M.A. González, P. Lindner, Macromolecules 41(4), 1364 (2008)

    Article  ADS  Google Scholar 

  24. R.H. Ebengou, J.P. Cohen-Addad, Polymer 35(14), 2962 (1994)

    Article  Google Scholar 

  25. L.C. Brunel, A. Caneschi, A. Dei, D. Friselli, D. Gatteschi, A.K. Hassan, L. Lenci, M. Martinelli, C.A. Massa, L.A. Pardi, F. Popescu, I. Ricci, L. Sorace, Res. Chem. Intermed. 28(2–3), 215 (2002)

    Article  Google Scholar 

  26. A. Maus, K. Saalwächter, Macromol. Chem. Phys. 208(19–20), 2066 (2007)

    Article  Google Scholar 

  27. M.I. Aranguren, Polymer 39(20), 4897 (1998)

    Article  Google Scholar 

  28. M. Giordano, P. Grigolini, D. Leporini, P. Marin, Phys. Rev. A 28(4), 2474 (1983)

    Article  ADS  Google Scholar 

  29. E.N. Ivanov, Sov. Phys. JETP 18(4), 1041 (1964)

    Google Scholar 

  30. L. Andreozzi, F. Cianflone, C. Donati, D. Leporini, J. Phys. Condens. Matter 8, 3795 (1996)

    Article  ADS  Google Scholar 

  31. A. Ottochian, D. Leporini, J. Non. Cryst. Solids 357, 298 (2011)

  32. A. Ottochian, C. De Michele, D. Leporini, J. Chem. Phys. 131, 224517 (2009)

    Article  ADS  Google Scholar 

  33. L. Andreozzi, M. Giordano, D. Leporini, J. Non-Cryst. Solids 235, 219 (1998)

  34. L. Larini, A. Barbieri, D. Prevosto, P.A. Rolla, D. Leporini, J. Phys. Condens. Matter 17, L199 (2005)

    Article  ADS  Google Scholar 

  35. A. Barbieri, G. Gorini, D. Leporini, Phys. Rev. E 69, 061509 (2004)

    Article  ADS  Google Scholar 

  36. F. Puosi, D. Leporini, J. Chem. Phys. 136, 041104 (2012)

    Article  ADS  Google Scholar 

  37. C. Schmidt, K.J. Kuhn, H.W. Spiess, Prog. Colloid Polym. Sci. 71, 71 (1985)

    Article  Google Scholar 

  38. V. Arrighi, S. Gagliardi, C. Zhang, F. Ganazzoli, J.S. Higgins, R. Ocone, M.T.F. Telling, Macromolecules 36(23), 8738 (2003)

    Article  ADS  Google Scholar 

  39. A. Chahid, A. Alegria, J. Colmenero, Macromolecules 27(12), 3282 (1994)

    Article  ADS  Google Scholar 

  40. N.V. Surovtsev, J.A.H. Wiedersich, V.N. Novikov, E. Rössler, A.P. Sokolov, Phys. Rev. B 58(22), 14888 (1998)

    Article  ADS  Google Scholar 

Download references

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Authors and Affiliations

  1. Istituto per i Processi Chimico-Fisici-Consiglio Nazionale delle Ricerche (IPCF-CNR), via G. Moruzzi 1, 56124, Pisa, Italy

    Carlo Andrea Massa, Luca Pardi, Monica Bertoldo & Dino Leporini

  2. Istituto di Chimica dei Composti Organometallici-Consiglio Nazionale delle Ricerche (ICCOM-CNR), via G. Moruzzi 1, 56124, Pisa, Italy

    Silvia Pizzanelli

  3. Department of Physics, University of Bucharest, Str. Atomistilor 405, Magurele, Jud. Ilfov, 077125, Bucharest, Romania

    Vasile Bercu

  4. Dipartimento di Fisica “Enrico Fermi”, Universitá di Pisa, Largo B. Pontecorvo 3, 56127, Pisa, Italy

    Dino Leporini

Authors
  1. Carlo Andrea Massa
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  2. Silvia Pizzanelli
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  3. Vasile Bercu
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  4. Luca Pardi
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  5. Monica Bertoldo
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  6. Dino Leporini
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Correspondence to Dino Leporini.

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Massa, C.A., Pizzanelli, S., Bercu, V. et al. A High-Field EPR Study of the Accelerated Dynamics of the Amorphous Fraction of Semicrystalline Poly(dimethylsiloxane) at the Melting Point. Appl Magn Reson 45, 693–706 (2014). https://doi.org/10.1007/s00723-014-0547-1

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  • DOI: https://doi.org/10.1007/s00723-014-0547-1

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