Abstract
Drying dissipative patterns of de-ionized suspensions (colloidal crystal state above the critical concentrations of crystallization) of the thermo-sensitive gels of poly(N-isopropylacrylamide) with degrees of cross-linking of 10% and 2% (pNIPAm(200–10) and pNIPAm(200–2)) were observed at 20 °C 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 micro-gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed. Microscopic drying structures of (a) flickering ordered spoke-lines, (b) ordered rings, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles are observed. The net and lattice structures formed more favorably at high degrees of cross-linking, at high concentrations of the gels, and/or high temperatures. By the addition of sodium chloride, very large dendrite-like and net structures of the large agglomerated particles formed at 20 °C and 45 °C, respectively. Importance of the cooperated convectional flow of the agglomerated particles during the drying processes is supported for the ordered array formation. The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrate surfaces during dryness are also important for the ordering. The microscopic drying patterns of gel spheres were different from those of linear type polymers and also from typical colloidal spheres, though the macroscopic patterns of gel system such as broad ring formation at the edges of the dried film were similar to other two systems.
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Acknowledgments
Financial supports to T.O. from the Ministry of Education, Culture, Sports, Science and Technology, Japan, for Exploratory Research and those for Scientific Research (B) to T.O., D.S., and A.T. from Japan Society for the Promotion of Science are greatly acknowledged. D.S. 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 T.O. are appreciated deeply. The authors thank Koji Horigome and Tomoyo Yamagata for their help in preparing the gel spheres. Hideki Kanoh is appreciated for his assistance of SPM measurements.
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Fig. S1
Drying patterns of pNIPAm(200–10) on a cover glass (0.1 ml, a–d), a watch glass (0.7 ml, e–h), and a glass dish (0.7 ml, i–l) at 20 °C. Humidity = 35%; (a, e, i) 2.37, (b, f, j) 0.711, (c, g, k) 0.119, and (d, h, l) 0.0474 wt.% (PDF 152 kb)
Fig. S2
Drying patterns of pNIPAm(200–2) on a cover glass (0.1 ml, a–d), a watch glass (0.7 ml, e–h), and a glass dish (0.7 ml, i–l) at 20 °C. Humidity = 35%; (a, e, i) 1.97, (b, f ,j) 0.591, (c, g, k) 0.0985, and (d, h, l) 0.0394 wt.% (PDF 171 kb)
Fig. S3
Microscopic drying patterns of pNIPAm(200–10) on a cover glass (a–d), a watch glass (e–h), and a glass dish (i–l) at 20 °C; 0.1 ml, 0.711 wt.% (a, e, i to d, h, l are the pictures from left edge to the right, the center to the right edge, and the center to the right edge, respectively; full scale is 200 μm (PDF 2436 kb)
Fig. S4
Microscopic drying patterns of pNIPAm(200–2) on a cover glass (0.1 ml, a–h), a watch glass (0.7 ml, i–l), and a glass dish (0.7 ml, m–p) at 20 °C; 1.97 wt.% (a–d), 0.591 wt.% (e–p), a, e to d, h are the pictures from the left edge to the right, i, m to l, p are the pictures from the center to the right edge; full scale is 100 μm (PDF 3016 kb)
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Okubo, T., Suzuki, D. & Tsuchida, A. Drying dissipative structures of thermo-sensitive gel spheres of poly(N-isopropylacrylamide). Influence of degree of cross-linking of the gels. Colloid Polym Sci 290, 867–877 (2012). https://doi.org/10.1007/s00396-012-2602-5
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DOI: https://doi.org/10.1007/s00396-012-2602-5