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Drying dissipative structures of thermosensitive gel spheres of poly (N-isopropylacrylamide). Influence of gel size

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Abstract

Drying dissipative patterns of de-ionized suspensions (colloidal crystal-state at high concentrations) of the thermosensitive gels of poly (N-isopropylacrylamide) with various sizes (ca. 400–1,500 nm in diameter at 20 °C) were observed at 20 and 45 °C on a cover glass, a watch glass, and a Petri glass dish. The broad rings were observed and their size decreased as gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed irrespective of gel size. The macroscopic flickering spoke-like patterns were observed for the gel spheres from 70 to 600 nm in diameter at 20 °C, but almost disappeared for extremely large spheres, poly(N-isopropylacrylamide)(1500-5). This work clarified the formation of the drying microscopic structures of (a) ordered rings, (b) flickering ordered spoke lines, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles. The ordered rings became rather vague as gel size increased. The large net structures formed so often for large gels. Size effect on the lattice patterns was not recognized so clearly. The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrate surfaces during dryness are important for the ordering. The microscopic drying patterns of gel spheres were quite different from those of linear type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation at the edges of the dried film were similar to each other.

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Acknowledgments

Financial supports to TO from the Ministry of Education, Culture, Sports, Science and Technology, Japan for Exploratory Research and those for Scientific Research (B) to TO, DS, and AT from Japan Society for the Promotion of Science are greatly acknowledged. DS also acknowledges Grand-in-Aid for Young Scientists (A) from the Ministry of Education, Culture, Sports, Science and Technology of Japan (22685024). The research funds from AMX Co. (Tokyo) to TO are appreciated deeply. The authors thank Tomoyo Yamagata and Koji Horigome for their help in preparing the gel spheres.

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Authors and Affiliations

  1. Institute for Colloidal Organization, Hatoyama 3-1-112, Uji, Kyoto, 611-0012, Japan

    Tsuneo Okubo

  2. International Young Researchers Empowerment Center, Shinshu University, 3-15-1 Ueda, Nagano, 386-8567, Japan

    Daisuke Suzuki

  3. Faculty of Textile Science & Technology, Shinshu University, Ueda, Nagano, 386-8567, Japan

    Daisuke Suzuki

  4. Department of Applied Chemistry, Faculty of Engineering, Gifu University, Gifu, Gifu, 501-1193, Japan

    Akira Tsuchida

Authors
  1. Tsuneo Okubo
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  2. Daisuke Suzuki
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  3. Akira Tsuchida
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Corresponding author

Correspondence to Tsuneo Okubo.

Electronic supplementary material

Fig. S1. Drying patterns of pNIPAm(400-5) (A), pNIPAm(600-5) (B) and pNIPAm(1500-5) spheres (C) on a cover glass {a–e (a, c), a–d (b), 0.1 ml}, a watch glass {f–j (a, c), e–h (b), 0.7 ml} and a glass dish {k–o (a, c), i–l (b), 0.7 ml} at 20 °C. Humidity = 35 %; a, f, k (a) 3.89 wt%; a, e, i (b) 3.88 wt%; a, f, k (c) 3.10 wt%; b, g, l (a) 0.97 wt%; b, f, j (b) 1.16 wt%; b, g, l (c) 0.78 wt%; c, h, m (a) 0.195 wt%; c, g, k (b) 0.194 wt%; c, h, m (c) 0.155 wt%; d, i, n (a) 0.052 wt%; d, h, l (b) 0.078 wt%; d, i, n (c) 0.0413 wt%; e, j, o (a) 0.0195 wt%; e, j, o (c) 0.0155 wt%

Fig. S2. Microscopic drying patterns of pNIPAm(400-5) (a), pNIPAm(600-5) (b) and pNIPAm(1500-5) (c) on a cover glass (a–d, 0.1 ml) a watch glass (e–h, 0.7 ml) and a glass dish (i–p, 0.7 ml) at 20 °C. Humidity = 35 %, a–h 0.97 wt% (a), 3.88 wt% (b), 0.78 wt% (c), i-l 3.89 wt% (a), 3.88 wt% (b), 3.10 wt% (c), m–p 0.97 wt% (a), 1.16 wt% (b), 0.78 wt% (c), a–d (a–c) are the pictures from the left edge to the right; e, i, m to h, l, p are from the center to the right edge, full scale is 100 μm

Fig. S3. Microscopic patterns of pNIPAm(400-5) (a), pNIPAm(600-5) (b) and pNIPAm(1500-5) gels (c) at 45 and 20 °C. Circles ordered ring, triangles ordered spoke-line, crosses net, squares lattice

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Okubo, T., Suzuki, D. & Tsuchida, A. Drying dissipative structures of thermosensitive gel spheres of poly (N-isopropylacrylamide). Influence of gel size. Colloid Polym Sci 290, 1901–1911 (2012). https://doi.org/10.1007/s00396-012-2727-6

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  • DOI: https://doi.org/10.1007/s00396-012-2727-6

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