Surface rheology of polymeric solids

Tisato Kajiyama, Keiji Tanaka, Noriaki Satomi, Atsushi Takahara

Research output: Contribution to journalArticlepeer-review


Surface molecular motions of amorphous polymeric solids have been directly measured on the basis of scanning viscoelasticity microscopic (SVM) and lateral force microscopic (LFM) measurements. SVM and LFM measurements were carried out for films of conventional monodisperse polystyrene (PS) with sec-butyl and proton-terminated end groups at room temperature. In the case of the number-average molecular weight, Mn, less than ca. 4.0 × 104, the surface was in a glass-rubber transition state even though the bulk glass transition temperature, Tg was far above room temperature, meaning that the surface molecular motion was fairly active compared with that in the bulk. LFM measurements of the monodisperse PS films at various scanning rates and temperatures revealed that the time-temperature superposition was applicable to the surface mechanical relaxation behavior and also that the surface glass transition temperature, Tgσ, was depressed in comparison with the bulk one even though the magnitude of Mn was fairly high at 1.40 × 105. The surface molecular motion of monodisperse PS with various chain end groups was investigated on the basis of temperature-dependent scanning viscoelasticity microscopy (TDSVM). The Tgσs for the PS films with Mn of 4.9 × 103 to 1.45 × 106 measured by TDSVM were smaller than those for the bulk one, with corresponding Mns, and the Tgσs for Mns smaller than ca. 4.0 × 104 were lower than room temperature (293 K). The active thermal molecular motion at the polymeric solid surface can be interpreted in terms of an excess free volume near the surface region induced by the surface localization of chain end groups. In the case of Mn = ca. 5.0 × 104, the Tgσs for the α,ω-diamino-terminated PS (α,ω-PS(NH2)2) and α,ω-dicarboxy-terminated PS (α,ω-PS(COOH)2) films were higher than that of the PS film. The change of Tgσ for the PS film with various chain end groups can be explained in terms of the depth distribution of chain end groups at the surface region depending on the relative hydrophobicity.

Original languageEnglish
Pages (from-to)239-248
Number of pages10
JournalChinese Journal of Polymer Science (English Edition)
Issue number3
Publication statusPublished - May 2000

All Science Journal Classification (ASJC) codes

  • General Chemical Engineering
  • Organic Chemistry
  • Polymers and Plastics


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