Water harvesting of bio-inspired micro/nano-structured spider silk
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摘要: 水是自然界大多数生物生存的必要条件，而动植物界存在着诸多奇妙的浸润现象。仿生微纳米复合材料浸润性相关研究是近年来国内外发展迅速的前沿热点，涉及跨领域、交叉领域。本文对仿生工程领域拥有集水性能的类蜘蛛丝微纳米复合材料的研究进展进行了评述，简要分析了材料的微纳米复合结构及其控制浸润性/液滴行为的机制，总结了类蜘蛛丝微纳米复合材料及集成蜘蛛网的制备技术发展(包括提拉法、静电纺丝法、微流体技术、三维编织技术、3D打印技术等)，展示了不同微纳米复合材料及相应集水性能。本文重点分析并对比了仿生蜘蛛丝微纳米复合材料的仿生结构设计、材料制备技术、集水性能等，并展望了拥有集水性能的微纳米复合材料在微流体芯片、天气预报、海水淡化、药物缓释、微反应器、能量储运与转换等多领域的进一步新兴、多功能化应用。Abstract: Water is necessary for organisms to survive in nature. In the animal and plant kingdoms, there are many interesting wetting phenomena. Recently, the research on the wettability of bio-inspired micro/nano-structured composites is an emerging and hot topic, which involves interdisciplinary and multidisciplinary subjects. This paper reviews the research progress of spider silk-like micro-composites with water collection for the field of bionic engineering. The micro/nano-structure and related mechanism for controlling wettability or liquid behaviours are briefly analysed. The fabricating and preparing methods of bio-inspired spider silk and integrated spider web are summarised, including dip-coating, electrospinning, micro-fluidics, 3D braiding, 3D printing, etc. The structure and fog harvesting ability of diverse micro/nano composites are displayed. This article also analyses and compares the bio-inspired structure design, fabricating and preparing technology, and water collection performance of diverse spider silk-like micro/nano composites. These composite materials which have water-harvesting function will have further or new applications in chips, weather forecast, seawater desalination, drug release, micro-reactor, energy storage and conversion, etc.
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Key words:
- bio-inspired /
- spider silk /
- micro/nano composites /
- water collection /
- droplet transport /
- wettability
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图 1 仿生集水结构单元的液滴受力分析示意图
Figure 1. Force analysis sketch of droplets on bio-inspired fog-harvesting units
FL—Laplace driving force; R1, R2—Radius of curvature at both ends of local spindle node; C—Capillary force on the droplet; Fs—Driving force; Wc—Capillary thickness; β—Half vertex of the spindle node; R1', R2'—Local curvature of the three phase contact line at both ends of the droplet along the spindle node; θ—Contact angle; θ1, θ2—Contact angle on material/location
图 3 结构多样性的仿生蜘蛛丝纤维：((a), (b)) 天然蜘蛛丝及提拉法制备的传统周期性纺锤节纤维[35]；((c)~(e)) 静电纺丝法制备的具有多孔、粗糙结构的纺锤节表面[51]；(f) 提拉法结合溶胶-凝胶技术制备的螺旋凹槽周期性纺锤节[53]；(g) 流体法制备的梯度尺寸纺锤节[64]；(h) 自组装二维星号交叉构筑[47]；((i), (j)) 微流体法制备的空心纺锤节纤维及其三维拓扑类蜘蛛网构筑[48]
Figure 3. Diverse bio-inspired spider silk: ((a), (b)) Natural spider silk and the traditional periodic spindle knot made using dip-coating[35]; ((c)-(e)) Porous/ rough spindle knot made using electrodynamic[51]; (f) Periodic spindle knot with spiral microgroove made using dip-coating with sol-gel technique[53]; (g) Spindle knot with gradient size made using fluid-coating[64]; (h) 2D self-assembly crossing design of artificial spider silk[47]; ((i), (j)) Hollow spindle knot made using microfluidics and the 3D artificial spider web[48]
图 2 近3年最新报道的较大规模的仿生集水网材：(a) 微纳米锥修饰三维多交叉结构仿生集水网材，被润湿后液滴低阻快速传播[45]；(b) 液滴在静电纺丝法制备的类蜘蛛网交叉丝上的合并行为[78]；(c) 液滴在微流体法制备的类蜘蛛网平行丝上的合并行为[79]
Figure 2. Bio-inspired large-scale fog-harvesting webs reported in the recent 3 years: (a) A novel 3D multi-intersectional network inspired by spider web, super low retention for liquid transport of wetted fibre[45]; (b) Droplet behaviour on crossing fibres of artificial spider web made with electrospinning[78]; (c) Droplet behaviour on parallel fibres of artificial spider web made with microfluid device[79]
N3D—Novel 3D multi-intersectional network; BNF-10—Bioinspired nanofibril-humped fibers (106 humps); BNF-20—Bioinspired nanofibril-humped fibers (212 humps); BNF-30—Bioinspired nanofibril-humped fibers (317 humps)
表 1 不同浸润性及黏附性质表面上的液滴接触状态及相应液滴行为
Table 1. Different surface contact states classified via wettability/adhesion property and corresponding liquid dynamics
Sketch Contact state Biological model Wettability and adhesion Liquid behaviour/trend 
Hydrophilic Tear film Hydrophilic, and highly adhesive Droplet can wet the surface or even spread flat 
Pinning Red rose petal; Salvinia (Super-)hydrophobic, but relatively high adhesion Droplet turns spherical, and stays still on the surface 
Slippery Lotus leaf (Super-)hydrophobic, and ultra-low adhesion Droplet turns spherical, and can easily leave the surface 
Anisotropic Butterfly wing; Rice leaf (Super)-hydrophobic, different retention force for different direction Droplet tends to directionally move 
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表 2 类蜘蛛丝材料制备技术总结
Table 2. Fabrication technologies of mimic spider silk
Method Advantages/features Sketcha Dip-coating Firstly developed to mimic artificial spider silks;
Easy to operate;
Can be combined with phase-separation avenues to control micro/nano-structures;
Can realise relatively large-scale preparation
Coaxial electrospinning/
electrodynamicSame composition of the knot with the host fibre;
Can be combined with wet-assembly techniques;
Can use/make bio-materials;
Can fabricate membrane on a substrate;
Can spin on other micro/nano-structured materials to optimise the function
Fluid-coating Mechanical automation;
Can prepare ultra-long fibres;
Modify the speed of motor to control the knot size;
Can prepare gradient structures by setting an acceleration of motor
Microfluidics Usually use biocompatible materials;
Can prepare relatively long fibres;
Can prepare hollow fibres;
Highly accurate and controllable
Mechanical or
textile approachAim to prepare large-scale water-collecting materials;
Can be combined with the above methods to enlarge the scale of materials;
Being a trend and a latest research direction (see details in subsection 3.2);
e.g., 3D printing/additive manufacturing (as shown in the right figure);
e.g., multi-dimensional multi-directional braid
Note: a—Sketch maps of dip-coating, electrodynamic, fluid-coating, and microfluidics are adapted with permission from[36].
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