Tunable, Fast, Robust Hydrogel Actuators Based on Evaporation- Programmed Heterogeneous Structures

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1 Supporting Information Tunable, Fast, Robust Hydrogel Actuators Based on Evaporation- Programmed Heterogeneous Structures Jinrong Wang 1, Jianfeng Wang*,1,2, Zhuo Chen 1, Shaoli Fang 2, Ying Zhu*,1, Ray H. Baughman 2 and Lei Jiang 1 1 Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, Beijing Key Laboratory of Bio-inspired Energy Materials and Devices, School of Chemistry and Environment, BeiHang University, Beijing, , China. 2 Alan G. MacDiarmid NanoTech Institute, University of Texas at Dallas, Richardson, TX 75083, USA. *Address correspondence to wangjianfeng@buaa.edu.cn, zhuying@buaa.edu.cn Figure S1. Element mapping of cross section of GO-clay-PNIPAM hydrogel at the site exposed to nitrogen gas. All elements from GO (carbon, oxygen), clay (silicon, magnesium, oxygen), PNIPAM (carbon, nitrogen, oxygen) were observed in both the dense layer and the porous layer. This indicates that GO, clay and PNIPAM did not separate from each other during the fabrication process. 1

2 Intensity (a.u.) GO GO-clay-PNIPAM θ (degree) Figure S2. Comparison of XRD curves of GO and heterogeneous GO-clay-PNIPAM hydrogel. The diffraction peak of GO at 2θ= 10.2o disappears in GO-clay-PNIPAM hydrogel. This indicates that GO was not aggregated during the fabrication process of the hydrogel. 50 µm Figure S3. SEM of the homogeneous porous structure of the hydrogel covered by mask. 2

3 b) a) 90 μm 90 μm 68 μm 393 μm 200 μm 100 μm Figure S4. Optical microscope images of global heterogeneous GO-clay-PNIPAM hydrogel at 20 C water (a) and 40 C water (b). The thickness of laminated layer indicated with red arrows did not change with temperature change. Differently, the thickness of porous layer indicated with white arrows shrunk from 393µm to 68µm when water temperature increased to 40 C. Figure S5. Masks with different shapes and sizes for fabricating segment-patterned (Figure S5 a,b) and stripe-patterned (Figure S5 c-f) heterogeneous GO-clay-PNIPAM hydrogel actuators. 3

4 Table S1. Data collection for Figure 2d in the main text. Bendable film actuator, including polymer film, porous film, electrospun mat and hydrogel film, are considered. In each cited paper, the most rapid bending velocity for comparison with our results is chosen. Thickness (mm) Curvature (mm -1 ) Time (s) Curvature thickness (mm mm -1 ) Curvature thickness time (s -1 ) Ref This work 0.03 foam

5 The data marked in yellow, black, pink and blue colours are porous film actuator, electrospun mat actuator, polymer film actuators and hydrogel film actuators respectively. 5

6 Table S2. Data collection for Figure 4h in the main text. Twistable film actuators are considered. In each cited paper, the most rapid twisting velocity for comparison with our results is chosen. Thickness (mm) Length (mm) Time (s) Twisting angle ( o ) Twisting angle thickness length ( o mm mm -1 ) Twisting angle thickness length time ( o s -1 ) Ref This work References (1) Zhao, Q.; Dunlop, J. W.; Qiu, X.; Huang, F.; Zhang, Z.; Heyda, J.; Dzubiella, J.; Antonietti, M.; Yuan, J., An instant multi-responsive porous polymer actuator driven by solvent molecule sorption. Nat. Commun. 2014, 5, (5), (2) Jiang, S.; Liu, F.; Lerch, A.; Ionov, L.; Agarwal, S., Unusual and Superfast Temperature- Triggered Actuators. Adv. Mater. 2015, 27, (33), (3) Dai, M.; Picot, O. T.; Verjans, J. M.; de Haan, L. T.; Schenning, A. P.; Peijs, T.; Bastiaansen, C. W., Humidity-responsive bilayer actuators based on a liquid-crystalline polymer network. ACS Appl. Mater. Interfaces 2013, 5, (11), (4) Shen, L.; Fu, J.; Fu, K.; Picart, C.; Ji, J., Humidity Responsive Asymmetric Free-Standing Multilayered Film. Langmuir 2010, 26, (22), (5) Wang Eun, L.; Jin, Y. J.; Lee Soon, P.; Giseop, K., Fluorescent Actuator Based on Microporous Conjugated Polymer with Intramolecular Stack Structure. Adv. Mater. 2012; p (6) Ma, Y.; Sun, J., Humido- and Thermo-Responsive Free-Standing Films Mimicking the Petals of the Morning Glory Flower. Chem. Mater. 2014, 21, (5). (7) Rana, S.; Cho, J. W.; Park, J. S., Thermomechanical and water-responsive shape memory properties of carbon nanotubes-reinforced hyperbranched polyurethane composites. J. Appl. Polym. Sci. 2013, 127, (4), (8) Cheng, F.; Yin, R.; Zhang, Y.; Yen, C. C.; Yu, Y., Fully plastic microrobots which manipulate objects using only visible light. Soft Matter 2010, 6, (15), (9) Jin, Y.; Paris, S. I.; Rack, J. J., Bending materials with light: photoreversible macroscopic deformations in a disordered polymer. Adv. Mater. 2011, 23, (37),

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