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Non-equilibrium disordered micelles observed after melting of crystalline-amorphous alternating lamellar structure in crystalline-amorphous block copolymers forming spherical morphology

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Abstract

The phase transitions from a crystalline-amorphous alternating lamellar structure (CA-LAM) to spheres arranged in a body-centered cubic (BCC) lattice in polybutadiene-poly(ε-caprolactone) block copolymers (PB-PCL) and binary mixtures of PB-PCL and PB homopolymers are investigated using small-angle X-ray scattering (SAXS). SAXS profiles with a broad first-order peak and a shoulder are obtained just after melting CA-LAM, but the SAXS profiles change into that of BCC upon further increasing the temperature. When the temperature exceeds the order-disorder transition temperature, the BCC lattice disappears and disordered micelles are observed. The SAXS profiles obtained just after melting CA-LAM resemble those of disordered micelles in the higher temperature region. As compared with the theoretical SAXS profiles based on the Percus-Yevick structure factor and the spherical form factor, the observed SAXS profiles are in excellent agreement with the calculated ones, indicating that the structure observed after melting CA-LAM is disordered micelles. The time-resolved isothermal SAXS measurements imply that disordered micelles after melting CA-LAM are only observed in the melting process. Thus, disordered micelles are the non-equilibrium transient structure observed only after melting CA-LAM.

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Acknowledgments

SAXS measurement was performed at the Photon Factory of High Energy Accelerator Research Organization (approval 2013G144) and at the SPring-8 (approval 2011B1157 and 2012B1139).

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Author notes

  1. Hideaki Takagi

    Present address: Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki, 305-0801, Japan

Authors and Affiliations

  1. Graduate School of Engineering, Department of Materials Science & Technology, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, 466-8555, Japan

    Hideaki Takagi, Yusuke Sugino, Shigeo Hara, Katsuhiro Yamamoto & Shigetaka Shimada

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  1. Hideaki Takagi
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  2. Yusuke Sugino
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  3. Shigeo Hara
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  4. Katsuhiro Yamamoto
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  5. Shigetaka Shimada
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Correspondence to Katsuhiro Yamamoto.

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This study received no funding.

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The authors declare that they have no competing interests.

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Takagi, H., Sugino, Y., Hara, S. et al. Non-equilibrium disordered micelles observed after melting of crystalline-amorphous alternating lamellar structure in crystalline-amorphous block copolymers forming spherical morphology. Colloid Polym Sci 294, 993–999 (2016). https://doi.org/10.1007/s00396-016-3851-5

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  • DOI: https://doi.org/10.1007/s00396-016-3851-5

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