Enhanced Glass Transition Temperature of Thin Polystyrene Films Having an Underneath Cross-Linked Layer

Lu Bai, Pan Luo, Xudong Yang, Jianquan Xu, Daisuke Kawaguchi, Cuiyun Zhang, Norifumi L. Yamada, Keiji Tanaka, Wei Zhang, Xinping Wang

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)


Due to the importance of the interface in the segmental dynamics of supported macromolecule ultrathin films, the glass transition temperature (Tg) of polystyrene (PS) ultrathin films upon solid substrates modified with a cross-linked PS (CLPS) layer has been investigated. The results showed that the Tg of the thin PS films on a silica surface with a ∼5 nm cross-linked layer increased with reducing film thickness. Meanwhile, the increase in Tg of the thin PS films became more pronounced with increasing the cross-linking density of the layer. For example, a 20 nm thick PS film supported on CLPS with 1.8 kDa of cross-linking degree exhibited a ∼35 and ∼50 K increase in Tg compared to its bulk and that on neat SiO2 substrate, respectively. Such a large Tg elevation for the ultrathin PS films was attributed to the interfacial aggregation states in which chains diffused through nanolevel voids formed in the cross-linked layer to the SiO2-Si surface. In such a situation, the chains were topologically constrained in the cross-linked layer with less mobility. These results offer us the opportunity to tailor interfacial effects by changing the degree of cross-linking, which has great potential application in many polymer nanocomposites.

Original languageEnglish
Pages (from-to)210-216
Number of pages7
JournalACS Macro Letters
Issue number2
Publication statusPublished - Feb 15 2022

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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