Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods

Rahmawati Rahmawati, Shiori Masuda, Chao Hung Cheng, Chigusa Nagano, Shuhei Nozaki, Kazutaka Kamitani, Ken Kojio, Atsushi Takahara, Naoki Shinohara, Kazuki Mita, Kiminori Uchida, Satoshi Yamasaki

Research output: Contribution to journalArticle

Abstract

The deformation behavior of polythiourethane (PTU) elastomers was investigated using in situ small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and X-ray absorption fine structure (XAFS) methods. Two PTUs were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane, and 1,4-butanedithiol (PTU-B) or 1,5-pentanedithiol (PTU-P). The effect of methylene length of the chain extender on molecular aggregation structure of PTU during the elongation process was evaluated. SAXS measurement revealed that the spacing of hard segment domains of PTUs increased and decreased in the directions parallel and perpendicular to the elongation direction and showed a constant value of strain above 2. The strain calculated from the spacing of the hard segment domains for PTU-B was larger than that for PTU-P, suggesting that well-developed hard segment domains were formed for PTU-B. WAXD measurement showed that strain-induced crystallization of the soft segment occurred at around the strain of 2. XAFS measurement showed that at the strain of 2 or 3, atoms in the vicinity of sulfur became more ordered, which is confirmed by the decrement of the extended XAFS Debye-Waller factor. It seems reasonable from these SAXS, WAXD, and XAFS results that the hard segment domains orientation occurred for both PTUs during the deformation process, followed by strain-induced crystallization of the soft segment. In addition, PTU-B exhibits more ordered hard segment domains that maintain their aggregation structure upon uniaxial deformation in comparison with PTU-P.

Original languageEnglish
Pages (from-to)6825-6833
Number of pages9
JournalMacromolecules
Volume52
Issue number18
DOIs
Publication statusPublished - Sep 24 2019

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Elastomers
X ray scattering
Diffraction
X ray absorption
Crystallization
X ray diffraction
Elongation
Agglomeration
Glycols
Cyclohexane
Sulfur
Atoms

All Science Journal Classification (ASJC) codes

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

Cite this

Rahmawati, R., Masuda, S., Cheng, C. H., Nagano, C., Nozaki, S., Kamitani, K., ... Yamasaki, S. (2019). Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods. Macromolecules, 52(18), 6825-6833. https://doi.org/10.1021/acs.macromol.9b00982

Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods. / Rahmawati, Rahmawati; Masuda, Shiori; Cheng, Chao Hung; Nagano, Chigusa; Nozaki, Shuhei; Kamitani, Kazutaka; Kojio, Ken; Takahara, Atsushi; Shinohara, Naoki; Mita, Kazuki; Uchida, Kiminori; Yamasaki, Satoshi.

In: Macromolecules, Vol. 52, No. 18, 24.09.2019, p. 6825-6833.

Research output: Contribution to journalArticle

Rahmawati, R, Masuda, S, Cheng, CH, Nagano, C, Nozaki, S, Kamitani, K, Kojio, K, Takahara, A, Shinohara, N, Mita, K, Uchida, K & Yamasaki, S 2019, 'Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods', Macromolecules, vol. 52, no. 18, pp. 6825-6833. https://doi.org/10.1021/acs.macromol.9b00982
Rahmawati, Rahmawati ; Masuda, Shiori ; Cheng, Chao Hung ; Nagano, Chigusa ; Nozaki, Shuhei ; Kamitani, Kazutaka ; Kojio, Ken ; Takahara, Atsushi ; Shinohara, Naoki ; Mita, Kazuki ; Uchida, Kiminori ; Yamasaki, Satoshi. / Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods. In: Macromolecules. 2019 ; Vol. 52, No. 18. pp. 6825-6833.
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AU - Rahmawati, Rahmawati

AU - Masuda, Shiori

AU - Cheng, Chao Hung

AU - Nagano, Chigusa

AU - Nozaki, Shuhei

AU - Kamitani, Kazutaka

AU - Kojio, Ken

AU - Takahara, Atsushi

AU - Shinohara, Naoki

AU - Mita, Kazuki

AU - Uchida, Kiminori

AU - Yamasaki, Satoshi

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N2 - The deformation behavior of polythiourethane (PTU) elastomers was investigated using in situ small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and X-ray absorption fine structure (XAFS) methods. Two PTUs were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane, and 1,4-butanedithiol (PTU-B) or 1,5-pentanedithiol (PTU-P). The effect of methylene length of the chain extender on molecular aggregation structure of PTU during the elongation process was evaluated. SAXS measurement revealed that the spacing of hard segment domains of PTUs increased and decreased in the directions parallel and perpendicular to the elongation direction and showed a constant value of strain above 2. The strain calculated from the spacing of the hard segment domains for PTU-B was larger than that for PTU-P, suggesting that well-developed hard segment domains were formed for PTU-B. WAXD measurement showed that strain-induced crystallization of the soft segment occurred at around the strain of 2. XAFS measurement showed that at the strain of 2 or 3, atoms in the vicinity of sulfur became more ordered, which is confirmed by the decrement of the extended XAFS Debye-Waller factor. It seems reasonable from these SAXS, WAXD, and XAFS results that the hard segment domains orientation occurred for both PTUs during the deformation process, followed by strain-induced crystallization of the soft segment. In addition, PTU-B exhibits more ordered hard segment domains that maintain their aggregation structure upon uniaxial deformation in comparison with PTU-P.

AB - The deformation behavior of polythiourethane (PTU) elastomers was investigated using in situ small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and X-ray absorption fine structure (XAFS) methods. Two PTUs were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane, and 1,4-butanedithiol (PTU-B) or 1,5-pentanedithiol (PTU-P). The effect of methylene length of the chain extender on molecular aggregation structure of PTU during the elongation process was evaluated. SAXS measurement revealed that the spacing of hard segment domains of PTUs increased and decreased in the directions parallel and perpendicular to the elongation direction and showed a constant value of strain above 2. The strain calculated from the spacing of the hard segment domains for PTU-B was larger than that for PTU-P, suggesting that well-developed hard segment domains were formed for PTU-B. WAXD measurement showed that strain-induced crystallization of the soft segment occurred at around the strain of 2. XAFS measurement showed that at the strain of 2 or 3, atoms in the vicinity of sulfur became more ordered, which is confirmed by the decrement of the extended XAFS Debye-Waller factor. It seems reasonable from these SAXS, WAXD, and XAFS results that the hard segment domains orientation occurred for both PTUs during the deformation process, followed by strain-induced crystallization of the soft segment. In addition, PTU-B exhibits more ordered hard segment domains that maintain their aggregation structure upon uniaxial deformation in comparison with PTU-P.

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