Hierarchical structure in nanoscale thin films of a poly(styrene-b- Methacrylate grafted with POSS) (PS214-b-PMAPOSS27)

Byungcheol Ahn, Tomoyasu Hirai, Sangwoo Jin, Yecheol Rho, Kwang Woo Kim, Masa Aki Kakimoto, Padma Gopalan, Teruaki Hayakawa, Moonhor Ree

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

An interesting organic-inorganic diblock copolymer, poly(styrene-b- methacrylate grafted with polyhedral oligomeric silsesquioxane) (PS-b-PMAPOSS), with PS (an average degree of polymerization DP of 214) and PMAPOSS (DP = 27) blocks was prepared: PS214-b-PMAPOSS27. The morphological structures in nanoscale thin films of PS214-b-PMAPOSS27 and their temperature-dependent changes were investigated in detail by performing grazing incidence X-ray scattering (GIXS) with a synchrotron radiation source. GIXS formulas based on structural models were derived for the quantitative analysis of the two-dimensional (2D) scattering data. In addition, the thermal properties of the diblock copolymer were characterized: it was found to be stable up to 330 °C, and to undergo a glass transition at 96 °C (PS block) and a melting transition at 173 °C (PMAPOSS block). The quantitative 2D GIXS analysis found that the diblock copolymer molecules in the thin films undergo phase separation into PS and PMAPOSS domains, which generates a lamellar structure. Surprisingly, in the solvent-annealed films with and without subsequent thermal annealing the lamellar structure is completely oriented in the out-of-plane of the film and is stable up to the degradation temperature. The PMAPOSS layers in the lamellar structure were found to consist of two sublayers, namely a densely ordered layer composed of vertically oriented orthorhombic crystals and a less ordered layer that consists of molecularly stacked layers that are oriented vertically. In both the sublayers, the PMAPOSS block chains have helical conformations and thus are present as molecular cylinders. These molecular cylinders are always oriented in the film plane. On heating, the orthorhombic crystals and the molecularly stacked layers melt over the range 170-190 °C. On subsequent cooling, the orthorhombic crystals and molecularly stacked layers are not fully recovered, which indicates that the formation of orthorhombic crystals and stacked layers in the PMAPOSS domains requires thermal annealing.

Original languageEnglish
Pages (from-to)10568-10581
Number of pages14
JournalMacromolecules
Volume43
Issue number24
DOIs
Publication statusPublished - Dec 28 2010
Externally publishedYes

Fingerprint

Styrene
Methacrylates
Lamellar structures
X ray scattering
Block copolymers
Thin films
Crystals
Annealing
Synchrotron radiation
Phase separation
Conformations
Glass transition
Melting
Thermodynamic properties
Polymerization
Scattering
Cooling
Heating
Degradation
Temperature

All Science Journal Classification (ASJC) codes

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

Cite this

Ahn, B., Hirai, T., Jin, S., Rho, Y., Kim, K. W., Kakimoto, M. A., ... Ree, M. (2010). Hierarchical structure in nanoscale thin films of a poly(styrene-b- Methacrylate grafted with POSS) (PS214-b-PMAPOSS27). Macromolecules, 43(24), 10568-10581. https://doi.org/10.1021/ma101276d

Hierarchical structure in nanoscale thin films of a poly(styrene-b- Methacrylate grafted with POSS) (PS214-b-PMAPOSS27). / Ahn, Byungcheol; Hirai, Tomoyasu; Jin, Sangwoo; Rho, Yecheol; Kim, Kwang Woo; Kakimoto, Masa Aki; Gopalan, Padma; Hayakawa, Teruaki; Ree, Moonhor.

In: Macromolecules, Vol. 43, No. 24, 28.12.2010, p. 10568-10581.

Research output: Contribution to journalArticle

Ahn, B, Hirai, T, Jin, S, Rho, Y, Kim, KW, Kakimoto, MA, Gopalan, P, Hayakawa, T & Ree, M 2010, 'Hierarchical structure in nanoscale thin films of a poly(styrene-b- Methacrylate grafted with POSS) (PS214-b-PMAPOSS27)', Macromolecules, vol. 43, no. 24, pp. 10568-10581. https://doi.org/10.1021/ma101276d
Ahn, Byungcheol ; Hirai, Tomoyasu ; Jin, Sangwoo ; Rho, Yecheol ; Kim, Kwang Woo ; Kakimoto, Masa Aki ; Gopalan, Padma ; Hayakawa, Teruaki ; Ree, Moonhor. / Hierarchical structure in nanoscale thin films of a poly(styrene-b- Methacrylate grafted with POSS) (PS214-b-PMAPOSS27). In: Macromolecules. 2010 ; Vol. 43, No. 24. pp. 10568-10581.
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