Abstract
Smart-controlled surface wettability from superhydrophilicity to superhydrophobicity has been extensively explored, and stimulus-responsive strategies have been widely accepted as a useful method to realize reversibility. However, achieving smart and precise wetting control remains challenging because most previous studies focused on stimulating single surface chemistry or microstructures. Herein, a dual-stimulus-responsive strategy that can synergistically stimulate surface chemistry and microstructures is demonstrated on the pH-responsive molecule poly(2-(diisopropylamino)ethyl methacrylate (PDPAEMA)-modified temperature-triggered shape memory polymer (SMP) arrays. The responsive PDPAEMA and SMP can provide the surface with tunable surface chemistry and microstructures, respectively. Thus, the wetting of the surface between various states can be reversibly and precisely controlled from superhydrophilicity to superhydrophobicity with contact angle (CA) differences of less than 15° under the cooperative effect between the adjustable surface microstructure and chemistry. The surface is further utilized as a platform to create gradient wettings based on its excellent controllability. Therefore, this work presents a strategy for surface wetting control by combining tunable surface microstructures and chemistry. The prepared samples with a special wetting controllability can be applied to numerous fields, including adaptive liquid microlenses, accurate drug release, and selective catalysis. This work also proposes novel expectations in designing smart functional surfaces.
摘要
近年来, 具有超亲水到超疏水转变的智能可控浸润性表面引 起了人们的广泛关注. 由于大多数报道仅采用单一的调控手段, 即 单一表面化学调控或单一的微结构调控, 表面浸润性的智能、精 细调控目前仍然很难实现. 本文中, 我们将pH响应的分子聚2-(二 异丙基氨基)甲基丙烯酸乙酯(PDPAEMA)修饰到温度响应的形状 记忆聚合物(SMP)阵列表面, 获得了一种可实现表面化学和微结构 协同调控的双刺激响应材料. 其中PDPAEMA (pH刺激)和SMP (温 度刺激)分别保证了表面化学和微结构的可调节性, 通过调节pH和 温度, 可使表面化学和表面微结构协同作用, 从而在所得表面上实 现超亲水到超疏水范围的智能可逆转变, 转变精度小于15°. 另外, 利用其优异的浸润性可控特性, 所得表面可用于制备梯度浸润性 控制平台. 本文所制备表面在自适应液体微透镜、精确药物释 放、选择性催化等领域具有良好的应用前景, 同时也为设计和开 发新型智能浸润性提供了参考.
Article PDF
Similar content being viewed by others
References
Lu Y, Sathasivam S, Song J, et al. Robust self-cleaning surfaces that function when exposed to either air or oil. Science, 2015, 347: 1132–1135
Wang S, Liu K, Yao X, et al. Bioinspired surfaces with super-wettability: New insight on theory, design, and applications. Chem Rev, 2015, 115: 8230–8293
Lou X, Huang Y, Yang X, et al. External stimuli responsive liquid-infused surfaces switching between slippery and nonslippery states: Fabrications and applications. Adv Funct Mater, 2020, 30: 1901130
Zhang H, Lai H, Cheng Z, et al. In-situ switchable super-hydrophobic shape memory microstructure patterns with reversible wettability and adhesion. Appl Surf Sci, 2020, 525: 146525
Wang Z, Zhang S, Gao S, et al. A simple, low-cost method to fabricate drag-reducing coatings on a macroscopic model ship. Chem Res Chin Univ, 2018, 34: 616–621
Chen L, Liu M, Bai H, et al. Antiplatelet and thermally responsive poly(N-isopropylacrylamide) surface with nanoscale topography. J Am Chem Soc, 2009, 131: 10467–10472
Sun M, Feng W, Wang B, et al. Studies on surface properties and cell adhesion properties of BSA modified DBM scaffold. Chem Res Chin Univ, 2019, 35: 700–707
Sheparovych R, Motornov M, Minko S. Low adhesive surfaces that adapt to changing environments. Adv Mater, 2009, 21: 1840–1844
Li C, Yu C, Hao D, et al. Smart liquid transport on dual biomimetic surface via temperature fluctuation control. Adv Funct Mater, 2018, 28: 1707490
Han K, Heng L, Zhang Y, et al. Slippery surface based on photoelectric responsive nanoporous composites with optimal wettability region for droplets’ multifunctional manipulation. Adv Sci, 2019, 6: 1801231
Wang B, Liang W, Guo Z, et al. Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: A new strategy beyond nature. Chem Soc Rev, 2015, 44: 336–361
Zhang J, Zhang F, Song J, et al. Electrospun flexible nanofibrous membranes for oil/water separation. J Mater Chem A, 2019, 7: 20075–20102
Leon AC, Imperial RES, Chen Q, et al. One-step fabrication of superhydrophobic/superoleophilic electrodeposited polythiophene for oil and water separation. Macromol Mater Eng, 2019, 304: 1800722
Yohe ST, Colson YL, Grinstaff MW. Superhydrophobic materials for tunable drug release: Using displacement of air to control delivery rates. J Am Chem Soc, 2012, 134: 2016–2019
Sun T, Wang G, Feng L, et al. Reversible switching between super-hydrophilicity and superhydrophobicity. Angew Chem Int Ed, 2004, 43: 357–360
Cheng M, Liu Q, Ju G, et al. Bell-shaped superhydrophilic-superhydrophobic-superhydrophilic double transformation on a pH-responsive smart surface. Adv Mater, 2014, 26: 306–310
Xiao M, Guo X, Cheng M, et al. pH-responsive on-off motion of a superhydrophobic boat: Towards the design of a minirobot. Small, 2014, 10: 859–865
Hong X, Gao X, Jiang L. Application of superhydrophobic surface with high adhesive force in no lost transport of superparamagnetic microdroplet. J Am Chem Soc, 2007, 129: 1478–1479
Lim HS, Lee SG, Lee DH, et al. Superhydrophobic to super-hydrophilic wetting transition with programmable ion-pairing interaction. Adv Mater, 2008, 20: 4438–4441
Zhu W, Zhai J, Sun Z, et al. Ammonia responsive surface wettability switched on indium hydroxide films with micro- and nanostructures. J Phys Chem C, 2008, 112: 8338–8342
Minko S, Müller M, Motornov M, et al. Two-level structured self-adaptive surfaces with reversibly tunable properties. J Am Chem Soc, 2003, 125: 3896–3900
Seo J, Lee JS, Lee K, et al. Switchable water-adhesive, super-hydrophobic palladium-layered silicon nanowires potentiate the angiogenic efficacy of human stem cell spheroids. Adv Mater, 2014, 26: 7043–7050
Krupenkin TN, Taylor JA, Wang EN, et al. Reversible wetting-dewetting transitions on electrically tunable superhydrophobic nanostructured surfaces. Langmuir, 2007, 23: 9128–9133
Lahann J, Mitragotri S, Tran TN, et al. A reversibly switching surface. Science, 2003, 299: 371–374
Gao W, Wang J, Zhang X, et al. Electric-tunable wettability on a paraffin-infused slippery pattern surface. Chem Eng J, 2020, 381: 122612
Qu R, Zhang W, Li X, et al. A smart nano-V2O5/ODA-coated mesh for a co-responsive photo-induced wettability transition and ROS generation for in situ water purification. J Mater Chem A, 2018, 6: 18003–18009
Caputo G, Cortese B, Nobile C, et al. Reversibly light-switchable wettability of hybrid organic/inorganic surfaces with dual micro-/nanoscale roughness. Adv Funct Mater, 2009, 19: 1149–1157
Zong C, Hu M, Azhar U, et al. Smart copolymer-functionalized flexible surfaces with photoswitchable wettability: From super-hydrophobicity with “rose petal” effect to superhydrophilicity. ACS Appl Mater Interfaces, 2019, 11: 25436–25444
Tian D, Zhang N, Zheng X, et al. Fast responsive and controllable liquid transport on a magnetic fluid/nanoarray composite interface. ACS Nano, 2016, 10: 6220–6226
Grigoryev A, Tokarev I, Kornev KG, et al. Superomniphobic magnetic microtextures with remote wetting control. J Am Chem Soc, 2012, 134: 12916–12919
Zhao S, Xia H, Wu D, et al. Mechanical stretch for tunable wetting from topological PDMS film. Soft Matter, 2013, 9: 4236–4240
Lee SG, Lee DY, Lim HS, et al. Switchable transparency and wetting of elastomeric smart windows. Adv Mater, 2010, 22: 5013–5017
Wu D, Wu SZ, Chen QD, et al. Curvature-driven reversible in situ switching between pinned and roll-down superhydrophobic states for water droplet transportation. Adv Mater, 2011, 23: 545–549
Zhu Y, Antao DS, Xiao R, et al. Real-time manipulation with magnetically tunable structures. Adv Mater, 2014, 26: 6442–6446
Chen CM, Yang S. Directed water shedding on high-aspect-ratio shape memory polymer micropillar arrays. Adv Mater, 2014, 26: 1283–1288
Wang L, Zhao Y, Tian Y, et al. A general strategy for the separation of immiscible organic liquids by manipulating the surface tensions of nanofibrous membranes. Angew Chem Int Ed, 2015, 54: 14732–14737
Li G, Hong G, Dong D, et al. Multiresponsive graphene-aerogel-directed phase-change smart fibers. Adv Mater, 2018, 30: 1801754
Jiang Y, Wan P, Smet M, et al. Self-assembled monolayers of a malachite green derivative: Surfaces with pH- and UV-responsive wetting properties. Adv Mater, 2008, 20: 1972–1977
Wang R, Xie T. Shape memory- and hydrogen bonding-based strong reversible adhesive system. Langmuir, 2010, 26: 2999–3002
Sarwate P, Chakraborty A, Garg V, et al. Controllable strain recovery of shape memory polystyrene to achieve super-hydrophobicity with tunable adhesion. J Micromech Microeng, 2014, 24: 115006
Schauer S, Meier T, Reinhard M, et al. Tunable diffractive optical elements based on shape-memory polymers fabricated via hot embossing. ACS Appl Mater Interfaces, 2016, 8: 9423–9430
Xu H, Yu C, Wang S, et al. Deformable, programmable, and shape-memorizing micro-optics. Adv Funct Mater, 2013, 23: 3299–3306
Ramaraju H, Akman RE, Safranski DL, et al. Designing biodegradable shape memory polymers for tissue repair. Adv Funct Mater, 2020, 30: 2002014
Zhao L, Zhao J, Liu Y, et al. Continuously tunable wettability by using surface patterned shape memory polymers with giant deformability. Small, 2016, 12: 3327–3333
Shahsavan H, Salili SM, Jákli A, et al. Smart muscle-driven self-cleaning of biomimetic microstructures from liquid crystal elastomers. Adv Mater, 2015, 27: 6828–6833
Wang W, Salazar J, Vahabi H, et al. Metamorphic super-omniphobic surfaces. Adv Mater, 2017, 29: 1700295
Lv T, Cheng Z, Zhang E, et al. Self-restoration of super-hydrophobicity on shape memory polymer arrays with both crushed microstructure and damaged surface chemistry. Small, 2017, 13: 1503402
Lv T, Cheng Z, Zhang D, et al. Superhydrophobic surface with shape memory micro/nanostructure and its application in rewritable chip for droplet storage. ACS Nano, 2016, 10: 9379–9386
Stratakis E, Mateescu A, Barberoglou M, et al. From super-hydrophobicity and water repellency to superhydrophilicity: Smart polymer-functionalized surfaces. Chem Commun, 2010, 46: 4136–4138
Feng L, Li S, Li Y, et al. Super-hydrophobic surfaces: From natural to artificial. Adv Mater, 2002, 14: 1857–1860
Zhao T, Nie FQ, Jiang L. Precise control of wettability from LCST tunable surface. J Mater Chem, 2010, 20: 2176–2181
Dang Z, Liu L, Li Y, et al. In situ and ex situ pH-responsive coatings with switchable wettability for controllable oil/water separation. ACS Appl Mater Interfaces, 2016, 8: 31281–31288
Xie T. Recent advances in polymer shape memory. Polymer, 2011, 52: 4985–5000
Puig J, Zucchi IA, Hoppe CE, et al. Epoxy networks with physical cross-links produced by tail-to-tail associations of alkyl chains. Macromolecules, 2009, 42: 9344–9350
Zhao Q, Qi HJ, Xie T. Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding. Prog Polym Sci, 2015, 49–50: 79–120
Lee CH, Kang SK, Lim JA, et al. Electrospun smart fabrics that display pH-responsive tunable wettability. Soft Matter, 2012, 8: 10238–10240
Wenzel RN. Resistance of solid surfaces to wetting by water. Ind Eng Chem, 1936, 28: 988–994
Cassie ABD, Baxter S. Wettability of porous surfaces. Trans Faraday Soc, 1944, 40: 546–551
Bellanger H, Darmanin T, Taffin de Givenchy E, et al. Chemical and physical pathways for the preparation of superoleophobic surfaces and related wetting theories. Chem Rev, 2014, 114: 2694–2716
Lafuma A, Quéré D. Superhydrophobic states. Nat Mater, 2003, 2: 457–460
Liu M, Wang S, Jiang L. Nature-inspired superwettability systems. Nat Rev Mater, 2017, 2: 17036
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21674030, 22075061 and 51790502), the Funding of Key Laboratory of Bioinspired Materials and Interfacial Science, the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, and China National Postdoctoral Program for Innovative Talents (BX20200106).
Author information
Authors and Affiliations
Contributions
Liu Y and Cheng Z conceived the idea; Jiang L revised the idea; Zhang D prepared the materials and conducted most of the measurements; Zhang D and Xia Q wrote the paper; Lai H revised the paper; Liu P performed most of the SEM characterizations; Zhang H analyzed the XPS results. All authors discussed the results and commented on the manuscript.
Corresponding authors
Additional information
Conflict of interest
The authors declare that they have no conflict of interest.
Dongjie Zhang received her BS degree (2014) and PhD degree (2020) at Harbin Institute of Technology, China. During 2018 to 2019, she stayed at the University of British Columbia in Canada as a visiting student in Mark MacLachlan’s group. She is currently a postdoc at the School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China. Her present research interest focuses on shape memory polymer with special wettability.
Zhongjun Cheng obtained his BS degree (2003) and MS degree (2006) in chemistry at Jilin University in Jilin, China, and PhD degree (2009) at the Institute of Chemisty, Chinese Academy of Sciences under the supervision of Prof. Lei Jiang. He is currently an associate professor at Harbin Institute of Technology, Harbin, China. His scientific interest is design and fabrication of superwetting materials with dynamic tunable micro-/nano-structures, and related applications.
Yuyan Liu obtained her BS and PhD degrees from the Department of Polymer Materials and Engineering, Harbin Institute of Technology, Harbin, China. During 2001 to 2002, she worked at the University of Tokyo in Japan as a visiting scholar. She is currently a professor at Harbin Institute of Technology. Her research interests include construction and intelligent control of micro-/nano-structure on polymer surface, spatial flexible rigid materials, shape memory polymer and composite materials, and recycling of polymer materials.
Rights and permissions
About this article
Cite this article
Zhang, D., Xia, Q., Lai, H. et al. Dual-responsive shape memory polymer arrays with smart and precise multiple-wetting controllability. Sci. China Mater. 64, 1801–1812 (2021). https://doi.org/10.1007/s40843-020-1554-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1554-y