Colloid and Polymer Science

, Volume 291, Issue 11, pp 2719–2724 | Cite as

Strain- and temperature-induced polymorphism of poly(dimethylsiloxane)

  • Masatoshi TosakaEmail author
  • Miki Noda
  • Kazuta Ito
  • Kazunobu Senoo
  • Koki Aoyama
  • Noboru Ohta
Short Communication


Phase behavior of silica-filled poly(dimethylsiloxane) (PDMS) network was investigated by wide-angle X-ray diffraction (WAXD) under various strain ratio between room temperature and −100 °C, and anomalous polymorphic behavior was discovered. At room temperature, when sufficient strain was applied, PDMS network was found to transform into the mesomorphic phase from which only a pair of sharp equatorial reflections and faint meridional scattering were obtained in the WAXD pattern. At low temperature, PDMS network crystallized into one of three different crystal forms according to strain ratio. These crystal forms were denoted as α, transient, and β forms in the descending order of corresponding strain ratio. The mesomorphic phase at room temperature transformed into the crystalline α form by reducing temperature. There was an anomalous feature about the transition of the crystalline forms that the position of reflections in the WAXD pattern changed continuously and reversibly with strain between the α and the β forms through the transient form, while keeping the diffraction angles almost unchanged.


Strain-induced crystallization Conformation Wide-angle X-ray diffraction Network polymer Skeletal structure Silicone rubber 



This study was partly supported by a Grant-in Aid for Scientific Research (C) no. 20550187 from Japan Society for the Promotion of Science (to M. Tosaka). The synchrotron radiation experiments were performed at the BL40XU of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (Proposal No. 2010B1215, 2012A1044, 2013A1203).

Supplementary material

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ESM 1 (PDF 460 kb)

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  1. 1.
    Owen MJ (1981) Why silicones behave funny. Chem Tech 11:288–292Google Scholar
  2. 2.
    Damaschun VG (1962) Röntgenographische Untersuchung der Struktur von Silikongummi. Kolloid-Z 180:65–67CrossRefGoogle Scholar
  3. 3.
    Schilling FC, Gomez MA, Tonelli AE (1991) Solid-state NMR observations of the crystalline conformation of poly(dimethylsiloxane). Macromolecules 24:6552–6553CrossRefGoogle Scholar
  4. 4.
    Albouy P-A (2000) The conformation of poly(dimethylsiloxane) in the crystalline state. Polymer 41:3083–3086CrossRefGoogle Scholar
  5. 5.
    Tosaka M, Senoo K, Sato K, Noda M, Ohta N (2012) Detection of fast and slow crystallization processes in instantaneously-strained samples of cis-1,4-polyisoprene. Polymer 53:864–872CrossRefGoogle Scholar
  6. 6.
    Ohlberg SM, Alexanders LE, Warrick EL (1958) Crystallinity and orientation in silicone rubber. I. X-ray studies. J Polym Sci 27:1–17CrossRefGoogle Scholar
  7. 7.
    Delides CG, Shepherd IW (1977) Crystallization in poly(dimethyl siloxane) networks formed by γ-irradiation. Polymer 18:97–98CrossRefGoogle Scholar
  8. 8.
    Murakami S, Senoo K, Toki S, Kohjiya S (2002) Structural development of natural rubber during uniaxial stretching by in situ wide angle X-ray diffraction using a synchrotron radiation. Polymer 43:2117–2120CrossRefGoogle Scholar
  9. 9.
    Toki S, Sics I, Ran S, Liu L, Hsiao BS, Murakami S, Senoo K, Kohjiya S (2002) New insights into structural development in natural rubber during uniaxial deformation by in situ synchrotron X-ray diffraction. Macromolecules 35:6578–6584CrossRefGoogle Scholar
  10. 10.
    Tosaka M, Murakami S, Poompradub S, Kohjiya S, Ikeda Y, Toki S, Sics I, Hsiao BS (2004) Orientation and crystallization of natural rubber network as revealed by WAXD using synchrotron radiation. Macromolecules 37:3299–3309CrossRefGoogle Scholar
  11. 11.
    Flory PJ (1947) Thermodynamics of crystallization in high polymers. I. Crystallization induced by stretching. J Chem Phys 15:397–408CrossRefGoogle Scholar
  12. 12.
    Yamamoto M, White JL (1971) Theory of deformation and strain-induced crystallization of an elastomeric network polymer. J Polym Sci Part A-2(9):1399–1415Google Scholar
  13. 13.
    Tosaka M (2009) A route for the thermodynamic description of strain-induced crystallization in sulfur-cured natural rubber. Macromolecules 42:6166–6174CrossRefGoogle Scholar
  14. 14.
    Wojdyr M (2010) Fityk: a general-purpose peak fitting program. J Appl Cryst 43:1126–1128CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Masatoshi Tosaka
    • 1
    Email author
  • Miki Noda
    • 2
  • Kazuta Ito
    • 2
  • Kazunobu Senoo
    • 2
  • Koki Aoyama
    • 3
  • Noboru Ohta
    • 3
  1. 1.Institute for Chemical ResearchKyoto UniversityUjiJapan
  2. 2.Sumitomo Bakelite Co. LtdKobeJapan
  3. 3.SPring-8 / JASRISayo-choJapan

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