液滴输运功能表面的仿生设计与制备研究进展

刘明; 陈少华

doi:10.6052/1000-0992-24-015

液滴输运功能表面的仿生设计与制备研究进展

doi: 10.6052/1000-0992-24-015 cstr: 32046.14.1000-0992-24-015

刘明¹,
陈少华^2, ,

1.
北京理工大学前沿交叉科学研究院, 北京 100081
2.
北京理工大学宇航学院, 北京 100081

基金项目: 国家自然科学基金 (12102041, 12472095, 12032004, 12293002) 资助项目

详细信息

作者简介:
刘明, 工学博士, 北京理工大学副教授、博导. 主要从事仿生功能表面设计与制备、表面/界面力学的研究, 在《Chem. Eng. J》《ACS Appl. Mater. Inter.》等国际SCI期刊发表论文20余篇, 授权/公开国际/国内发明专利10项, 曾获得北京力学会青年力学工作者优秀论文奖、北京市优秀毕业生、英国皇家化学会优秀成果展示奖等. 担任《Appl. Sci.-Basel》期刊客座编辑以及《J Bionic Eng.》《Adv. Bionics》期刊青年编委

陈少华, 工学博士, 北京理工大学特聘教授. 主要从事仿生材料与结构力学, 表/界面与薄膜力学, 微纳米与多尺度力学方向的研究. 已发表SCI论文210余篇, 出版专著2部, 授权专利6项, 多年评为爱思维尔中国高被引学者. 曾获国家自然科学二等奖1项(3/3), 中国力学学会自然科学一等奖1项(1/3), 江苏省力学学会科学技术一等奖1项(2/5), 茅以升北京青年科技奖, 中国力学学会青年科技奖等, 获国家杰出青年科学基金, 入选万人计划领军人才、中青年科技创新领军人才、国家百千万人才工程, 并被授予有突出贡献中青年专家, 国务院政府特殊津贴专家等称号. 现任中国力学学会理事, 中国复合材料学会常务理事, 北京力学会常务理事, 《固体力学学报》副主编, 《力学学报》《力学进展》《J. Adv. Biotech. & Bioeng.》《Nano Materials Science》《Scientific Report》《Biomimetics》等期刊编委

通讯作者:
shchen@bit.edu.cn , shchen@bit.edu.cn

中图分类号: O341
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出版历程
- 收稿日期: 2024-04-29
- 录用日期: 2024-06-26
- 网络出版日期: 2024-07-03
- 刊出日期: 2024-09-25

Research progress of biomimetic design and preparation of functional surfaces for droplet transport

LIU Ming¹,
CHEN Shaohua^{2
, ,}

1.
Advanced Research Institute of Multi-Disciplinary Sciences, Beijing Institute of Technology,Beijing 100081, China
2.
School of Aerospace Engineering, Beijing Institute of Technology, Beijing 100081, China

More Information

Corresponding author: shchen@bit.edu.cn , shchen@bit.edu.cn

摘要

摘要: 液滴输运功能表面在绿色能源、医疗科技、新材料等领域具有重要应用, 例如雾中淡水收集、药物靶向治疗等. 自然界具有多种可实现液滴定向运输与定点转移的生物表面, 为液滴输运功能表面的设计与制备提供了绝美的范例, 已涌现出大量新颖的、巧妙的仿生设计研究成果. 本文首先概括总结了自然界具有自发输运液滴的典型生物体功能表面, 阐述了表征固体表面浸润性相关的基础理论; 其次, 综述了不同自驱动机制下液滴输运功能表面的仿生研究进展, 对比分析了不同功能表面的液滴自驱动机理及影响因素; 进一步分类阐述和分析了磁场、电场、温度场等外场调控实现液滴定向运输或定点转移功能表面的研究现状; 最后归纳总结了此类仿生功能表面在实际工程中的应用, 并对该方向的研究前景和发展趋势提出展望.
- 液滴输运 /
- 功能表面 /
- 仿生设计与制备 /
- 表面浸润性 /
- 外场调控
Abstract: Functional surfaces for droplet transport has important applications in green energy, medical technology, new materials and other fields, such as fog collection, drug targeted therapy, etc. The surfaces of natural creatures with specific functions of directional transport and fixed-point transfer of droplets provide excellent examples for design and preparation of functional surfaces for droplet transport, a large number of novel and flexible bionic research achievements have been arisen. Firstly, the typical surfaces of natural creatures with self-driven functions of droplet transport are summarized and the basic theories of wettability on solid surface are elaborated; then, the biomimetic research progress of functional surfaces for droplet transport based on different self-driven mechanism is reviewed, the mechanism and influencing factors of droplet transport on different functional surfaces are compared and analyzed; furthermore, the current research of the functional surface for directional transport or fixed-point transfer of droplet under the action of external field such as magnetic field, electric field, temperature field and etc. are elaborated and analyzed; finally, the applications and future directions of such biomimetic functional surfaces are summarized and prospected.
- droplet transport /
- functional surface /
- biomimetic design and preparation /
- surface wettability /
- stimulus of external field

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图 1 自然界生物表面的液滴输运/转移及其仿生研究概述(Ju et al. 2014, Feng et al. 2021, Parker & Lawrence 2001, Hamilton & Seely 1976, 江雷和冯琳 2007, Guadarrama-Cetina et al. 2014, Nørgaard & Dacke 2010, Kennedy 1970, Prakash et al. 2008, Bohn & Federle 2004, Chen et al. 2016, Box et al. 2019, Feng et al. 2020)

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图 2 固体微颗粒的输运、转移和旋转. (a) 微结构形貌及固体微颗粒的定向输运(Li et al. 2022, 李程浩 2022), (b) 不同形状固体微颗粒在空气中和水下的输运、转移和筛选(Li et al. 2021, 李程浩 2022), (c) 应变梯度驱动固体微颗粒定向输运和定点旋转(Wang & Chen 2015, Khan et al. 2020), (d) 范德华力作用下筛选固体微颗粒混合物的纳米筛(王帅 2018, Wang et al. 2018)

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图 3 固体表面的液滴浸润状态. (a) 液滴在光滑平面, (b) Wenzel浸润状态, (c) Cassie-Baxter状态, (d) 滚动角, (e) 前进角和后退角

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图 4 (a) Cassie状态向Wenzel状态转变(Papadopoulos et al. 2013), (b) 具有任意轮廓微结构表面的浸润模型(Guo et al. 2016), (c) 浸润系统的吉布斯自由能变化规律与稳定性阈值(Guo et al. 2016), (d1) ~ (d2) 微结构侧面粗糙度对液滴压缩和释放的影响(黄立阳 2021), (e) Wenzel状态向Cassie状态转变(Wang et al. 2020)

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图 5 液滴自发输运模型. (a) 圆锥模型(Lorenceau & Quéré 2004), (b) 仿鸟喙模型(Prakash et al. 2008), (c) 猪笼草表面非对称沟槽结构及其定向输运液滴 (Chen et al. 2016), (d1) ~ (d2) 双面锥形结构阵列及液滴定向输运行为(Feng et al. 2020), (e) 倾斜微柱浸润模型(李兴济 2019), (f) 浸润梯度表面的圆形三相接触线(Subramanian et al. 2005), (g) 浸润梯度表面的非圆形三相接触线(Li et al. 2019), (h) 楔形梯度表面的圆形三相接触线(Alheshibri et al. 2013), (i) 液滴铺展输运的理论模型(Khoo & Tseng 2009), (j) 液滴滑动输运的理论模型(Liu et al. 2020b)

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图 6 浸润梯度表面液滴的定向输运. (a1) ~ (a10) 俯视图 (b1) ~ (b10) 侧视图(Liu et al. 2019)

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图 7 形状梯度表面的液滴定向输运. (a) 数值结果(Wang et al. 2019)和 (b) 实验结果(Liu et al. 2019, 刘明 2020), (c) ~ (e) 多级结构图案、曲线路径和螺旋路径上的液滴输运(Liu et al. 2019, 刘明 2020)

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图 8 (a) 表面接触角随砂纸颗粒尺寸的变化(Liu et al. 2020a), (b) 含润滑区的楔形梯度表面, (c) ~ (d)液滴定向滑动行为的全局视野和底部视野(Liu et al. 2020a, Liu et al. 2020b)

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图 9 磁场调控功能表面的液滴定向输运. (a) 非对称微结构表面的各向异性浸润(Zhu et al. 2014), (b) 磁性微柱阵列利用弯曲变形驱动液滴定向输运(Lin et al. 2018), (c) 倾斜微结构阵列表面的液滴单向滑动输运(Cao et al. 2017), (d) 超疏水磁性薄膜利用宏观变形实现液滴输运和汇聚(Chen et al. 2018, Chen et al. 2019)

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图 10 磁场调控功能表面的液滴定点转移. (a) 表面浸润状态在Cassie和Wenzel之间切换(Hou et al. 2017), (b) 液滴与无规则毛发状微结构表面的点接触与线接触(Yang et al. 2018), (c) 液滴沿任意可控路径的定点转移(Liu et al. 2022a), (d) 仿生“机械手”无损、定点转移液滴(Liu et al. 2022b)

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图 11 电场调控功能表面的液滴定向输运. (a) 静电吸力驱动液滴定向输运(Mertaniemi et al. 2011), (b) 液滴沿C形路径的定向输运(Dai et al. 2019), (c) 电场梯度表面液滴定向输运(Li et al. 2020), (d) 矩形、正弦型和月牙形电极驱动液滴单向输运(Rajabi & Dolatabadi 2010)

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图 12 电场调控功能表面的液滴定点转移. (a) 新月牙形电极驱动液滴往复输运(Jin 2016), (b) 电荷密度梯度作用下的液滴输运和转移(Sun et al. 2019), (c) 电场驱动弹性体薄膜表面浸润状态转变及液滴定点转移(Li et al. 2020), (d) 自供电液滴输运系统(Nie et al. 2018)

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图 13 光热效应调控功能表面的液滴定向输运. (a) 温度场中非对称棘轮结构驱动液滴定向输运(Grounds et al. 2012), (b) 激光照射下微结构演变及其各向异性浸润性(Oscurato et al. 2017), (c) 微流管光热效应及液滴定向输运(Geng et al. 2018), (d) V型非对称微结构阵列表面的液滴定向输运(Zhang et al. 2020)

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图 14 光热效应调控功能表面的液滴定点转移. (a) 有机凝胶表面液滴沿任意路径定点转移(Gao et al. 2018), (b) 石墨烯海绵膜表面液滴沿可编程输运轨道定点转移(Wang et al. 2018), (c) 仿生睡莲气孔制备的水凝胶定点转移液滴(Sun et al. 2020), (d) 仿生温控薄膜表面液滴定点转移(Zhang et al. 2021)

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图 15 (a) 蜂窝状共聚物表面驱动液滴定向输运(Zhang et al. 2020), (b) 拉伸应变作用下水滴和油滴的定点转移(Wang et al. 2017), (c) 垂直振动激励下的液滴定向输运(Duncombe et al. 2012), (d) 水平振动激励下的液滴单向输运(Wu et al. 2020)

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图 16 (a) 振动激励下液滴在周期性排列浸润梯度表面的定向输运(Qi et al. 2019), (b) ~ (c) 声表面波驱动液滴定向输运(Luo et al. 2017, Sun et al. 2020)

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图 17 雾中集水和油水分离应用. (a) 仿生树杈多级结构雾中集水(Wang et al. 2017), (b) 仿生沙漠甲虫背部雾中集水(Liu et al. 2020a), (c) 疏水/亲水协同Janus集水系统(Cao et al. 2015), (d) 仿生仙人掌刺锥形结构油水分离(Li et al. 2013), (e) pH值可调的网状编织物油水分离(Yan et al. 2018), (f) 仿生南洋杉叶棘齿结构油水分离(Feng et al. 2021)

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表 1 符号的物理意义

γ_SL — 固-液界面张力	β₁ — 微结构轴线与壁面切线夹角
γ_LG — 气-液界面张力	β₂ — 微结构轴线与气-液界面切线夹角
γ_SG — 固-气界面张力	ΔP_r — 毛细压强
θ_Y — 本征接触角	Δp — 液体与气体压强差
θ_a — 表观接触角	S — 微柱截面面积与周长之比
θ_ad — 前进角	S_Horizon — 气-液界面面积
θ_re — 后退角	L_Horizon — 三相接触线长度的投影
θ_E — 纳米结构壁面本征接触角	k_g — 三相接触线的测地曲率
θ — 纳米结构壁面表观接触角	V₀ — 液滴体积
θ_c — 临界接触角	F — 三相接触线的拐角弧长
f₁ — 固-液界面面积分数	E — 三相接触线的边界线长度
f₂ — 气-液界面面积分数	H — 压板与微结构顶部间距
r — 表面粗糙度	H_cr — 临界高度
r₀ — 微结构截面的等效圆半径	ρ — 液体密度
R_c — 三相接触线拐角处的曲率半径	g — 重力加速度
R — 浸润半径	m — 液滴质量
κ₁ — 平面结构的壁面母线曲率	w — 液滴宽度
κ₂ — 空间空穴结构的壁面母线曲率	k — 比例常数
κ₃ — 空间凸起结构的壁面母线曲率	l_cr — 特征长度
α — 滚动角	λ — 三相接触线的线张力
Γ — 线张力系数, 量纲为N	f_c、d、β_t0 — 微结构几何参数
注：固体表面浸润理论式(1)~式(15)中各类符号的物理意义.

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表 2 液滴定向输运的驱动力、输运位移及速度表达式

驱动类型	驱动力	输运位移	输运速度
曲率梯度	A^*	—	—
曲率梯度	B^*	L_b	—
非对称微结构	C^*	J^*	—
非对称微结构	D^*	—	—
浸润梯度	E^*	—	—
浸润梯度	F^*	K^*	O^*
形状梯度	G^*	L^*	—
	H^*	M^*	数值结果, 输运位移的微分
	I^*	N^*	—
注:
${{A}}^*=\displaystyle\int_{ { {R}_{{\mathrm{S}}} } }^{ { {R}_{{\mathrm{L}}} } }{ {2\gamma }/{ { {\left( R+{ {R}_{0} } \right)}^{2} } }\;}\sin \alpha {\mathrm{d}}z$, R_L、R_S分别为圆锥横截面半径, α为0.5倍锥角, γ为液体表面张力, (Ju et al. 2014, Lorenceau & Quéré 2004, Zhang & Han 2007).
${{B}}^*=\gamma WL/x $, W为平板宽度, L为液膜长度, x为液滴和喙根之间距离, L_b为平板 (鸟喙) 长度, (Prakash et al. 2008).
$ {{C}}^*=2H\left(x\right)\cdot\left(-\gamma\cos\theta_{\mathrm{a}}\right)+\rho gx \left[\dfrac{\alpha_1}{2}H^2\left(x\right)-\dfrac{\left(\alpha_1-\alpha_2\right)}{3h}H^3\left(x\right)\right] $ (系统能量),
${{J}}^*=\dfrac{2\gamma \cos { {\theta }_{{\mathrm{a}}} } }{\rho gx{ {\alpha }_{1} } }+\dfrac{ { {\alpha }_{1} }-{ {\alpha }_{2} } }{ { {\alpha }_{1} }h}\dfrac{4{ {\gamma }^{2} }{ {\cos }^{2} }{ {\theta }_{{\mathrm{a}}} } }{ { {\rho }^{2} }{ {g}^{2} }{ {x}^{2} }\alpha _{1}^{2} }+\cdots \cdots$, θ_a为表观接触角, ρ为液体密度, g为重力加速度, α₁和α₂分别为仿生猪笼草结构的几何角度, H(x)为位置x处的液滴输运位移, (Chen et al. 2016).
$ {{D}}^*=\ \left(9\pi\right)^{1/3\; }\gamma\Omega^{2/3\; }4^{1/3\; }\left[2-3\cos\theta_{\mathrm{a}}+\cos^3\theta_{\mathrm{a}}\right] \left[\left(1-\cos\theta_{\mathrm{a}}\right)^{4/3\; }\left(2+\cos\theta_{\mathrm{a}}\right)^{2/3\; }\right]^{-1} $ (自由能), Ω为液滴体积, (Feng et al. 2020).
${{E}}^*= 2R\gamma \displaystyle\int_{0}^{\pi /2}{\left[ \cos {{\left( {{\theta }_{{\mathrm{Y}}}} \right)}_{{\mathrm{f}}}}-\cos {{\left( {{\theta }_{{\mathrm{Y}}}} \right)}_{{\mathrm{r}}}} \right]}\cos \phi {\mathrm{d}}\phi $, θ_Y为不同区域的本征接触角, R为液滴半径, r、f分别表示液滴前缘、后缘, (Subramanian et al. 2005).
${{F}}^*= 2l(t)\gamma \left\{ {{\left[ \cos {{\theta }_{{\mathrm{Y}}}}\text{-}\cos {{\theta }_{{\mathrm{ad}}}} \right]}_{{\mathrm{f}}}}-{{\left[ \cos {{\theta }_{{\mathrm{Y}}}}\text{-}\cos {{\theta }_{{\mathrm{re}}}} \right]}_{{\mathrm{r}}}} \right\} $,
${{K}}^*=0.06\gamma /2784.67m\left[ {{\left( \cos {{\theta }_{{\mathrm{r}}}}-\cos {{\theta }_{{\mathrm{ad}}}} \right)}_{r}}-{{\left( \cos {{\theta }_{{\mathrm{l}}}}-\cos {{\theta }_{{\mathrm{re}}}} \right)}_{{\mathrm{l}}}} \right]\left( {{{\mathrm{e}}}^{52.77t}}-52.77t-1 \right) $,
${O}^*=\dfrac{{0.06{\gamma _{\rm {LG}}}}}{{52.77m}}\left[ {\left( {\cos {\theta _{\rm r}} - \cos {\theta _{\rm {ad}}}} \right)_{\rm r}} - {\left( {\cos {\theta _{\rm l}} - \cos {\theta _{{\rm {re}}}}} \right)_{\rm l}} \right]\left( {{\rm e}^{52.77t}} - 1 \right)$, θ_Y为不同区域的本征接触角, θ_ad、θ_re分别为前进角和后退角, l为液滴覆盖的不同浸润区域交界线长度, t为输运时间, m为液滴质量, (Liu et al. 2019).
${{G}}^*= 2R\gamma \left( \cos {{\theta }_{\text{philic}}}-\cos {{\theta }_{\text{phobic}}} \right)\left( \sin {{\phi }_{{\mathrm{B}}}}-\sin {{\phi }_{{\mathrm{F}}}} \right) $,
${ L}^*=\sqrt[3]{V}{\tan ^2}\dfrac{1}{2}\alpha \left( {1 + \tan \dfrac{1}{2}\alpha } \right){\left[ \dfrac{1}{3}\left( {\dfrac{{{\theta _{{\rm{philic}}}}}}{{{{\sin }^2}{\theta _{{\rm{philic}}}}}} - \cot {\theta _{{\rm{philic}}}}} \right) + \dfrac{\pi }{6}\tan \dfrac{1}{2}\alpha \left( {\dfrac{2}{{\sin {\theta _{{\rm{philic}}}}}} + \cot {\theta _{{\rm{philic}}}}} \right){\left( {\dfrac{1}{{\sin {\theta _{{\rm{philic}}}}}} - \cot {\theta _{{\rm{philic}}}}} \right)^2} \right]^{ - \tfrac{1}{3}}}$, θ_philic、θ_phobic分别为亲水区、疏水区表观接触角, R为圆形三相接触线半径, V为液滴体积, α为楔形顶角角度, Φ_b、Φ_f分别为极角, (Alheshibri et al. 2013, Liu et al. 2019).

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${{H}}^ *=4 \gamma \phi_{\mathrm{p}} \operatorname{tr} \phi_2 / R_{\mathrm{eff}}$,
${{M}}^*= \dfrac{{\mathrm{d}}^2Y}{{\mathrm{d}}t^2}+\dfrac{\eta {\mathrm{r}}}{\rho V}\left\{\dfrac{8\phi_{\mathrm{pt}}\left[\sin\phi_2(Y+r)-\sin\phi_{{\mathrm{2o}}}(Y_{\mathrm{o}}+r)\right]}{(kR_{{\mathrm{eff}}})^2}\right\} \dfrac{{\mathrm{d}}Y}{{\mathrm{d}}t}-\dfrac{4r\gamma_{{\mathrm{LV}}}}{\rho V}\left[\dfrac{\phi_{\mathrm{p}}\phi_{\mathrm{2t}}}{kR_{{\mathrm{eff}}}}\right]=0 $, Φ_pf为孔隙体积比, t为纳米纤维总厚度, r为圆形足迹半径, Φ₂为极角, R_eff为理想中空圆柱体的有效半径, (Khoo & Tseng 2009).
${{I}}^*= l\gamma \left\{ \left( \cos \theta -\cos {{\theta }_{\text{0}}} \right)\text{+}\left[ \cos{{\theta }_{{\mathrm{r}}}}\left( x \right)-\cos{{\theta }_{{\mathrm{f}}}}\left( x \right) \right] \right\} $,
${{N}}^*=\sqrt[3]{\dfrac{3V{{\sin }^{3}}\theta }{\pi \left( 2+\cos \theta \right){{\left( 1-\cos \theta \right)}^{2}}}}\left( \csc \dfrac{1}{2}\alpha +1 \right)$, θ₀、θ分别为超疏水区和楔形区静态接触角, θ_f(x)、θ_r(x)表示水滴前缘和后缘的瞬时接触角, α为楔形顶角角度, (Liu et al. 2020b).

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