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Materials Today: Proceedings 3 (2016) 696 702

Advances in Functional Materials (Conference 2015), AFM 2015

Bioinspired Structure Materials to Control Water-collecting

Properties
Miaoxin Zhang, Yongmei Zheng*
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education,School of Chemistry and Environment,
Beihang University, Beijing 100191, China.

Abstract

Natural evolution endows biological surfaces with unique wettability. The capture silk of a cribellate spider can collect
tiny droplets directionally through a cooperation of curvature- and wettable gradients in periodic spindle-knot
structures. Inspired by the role of micro- and nanostructures in water collecting ability of spider silk, some functional
spindle-knotted fibers are designed by using various methods, including dip/fluid-coating, electrospinning, wetassembly and micro-fluidic technology. These smart artificial fibers exhibit various water-collecting properties, such
as efficient water-collecting, long-distance droplet transport, and intelligent responses to external stimulus (e.g.,
temperature, illumination, humidity). The studies are significant in potential application.
Copyright 2014 Elsevier Ltd. All rights reserved.

2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of Conference Committee Members of Advances in Functional Materials
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
(Conference
2015).
Selection
and peer-review
under responsibility of Conference Committee Members of Advances in Functional Materials (Conference 2015).
Keywords:bioinspired; water collection; micro- and nanostructure; wettability; spider silk.

1. Introduction
Many biological surfaces, after million years of evolution in nature, exhibit a capability of controlling droplet
behavior, such as spider silk [1], beetles back [2, 3], lotus leaf [4, 5], butterfly wings [6],cactus [7], geese feather [8],
Nepenthes [9], rice leaf [10] etc. Recently, spider silks have attracted peoples attention again due to their superior
water collection ability [11-14]. It is found that with cooperation of geometry structure and wettable gradient, the
spindle-knot of silk can transport tiny droplets directionally, which is significant to design and fabricate more

* Corresponding author.Tel.: +86-10-82338212; fax: +86-10-82338212.

E-mail address:zhengym@buaa.edu.cn

2214-7853 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and peer-review under responsibility of Conference Committee Members of Advances in Functional Materials (Conference 2015).
doi:10.1016/j.matpr.2016.01.115

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697

functional materials. In this review, we described how to mimic the spindle-knot structure of natural spider silk by
using various strategies, and presented the potential applications of some artificial spindle-knotted fibers.

2. Mimic nature spider silk

As shown in Figure 1a, a capture silk of cribellate spider is characterized by periodic puffs and joints surrounding
two main-axis fibers [1]. After absorbing water, interestingly, a wet-rebuilt happens. Original puff structures deform
to spindle-knots, thus the wet spider silk is composed of alternate spindle-knots and joints (apex angles 19o) with a
periodicity of ~89.3 13.5 m. The diameters of spindle-knot and joint are ~21.0 2.7 m and ~5.9 1.2 m,
respectively. This unique geometry structure endows the wet-spider silk with a directional water-collecting ability,
which originates from two driving forces-Laplace pressure difference and surface energy gradient. As presented in
Figure 1a, due to conical structure, there exists a Laplace pressure difference (P) acting on a droplet:

(1)


Where r is the local radius; R0 is the droplet radius; is the half apex-angle of spindle-knot, and z is the integrating
variable along the diameter of spindle-knot. Besides, the spindle-knot is composed of highly random nanofibrils, while
the joint is composed of relatively aligned nanofibrils, therefore, the spindle-knot region has a higher roughness than
joint region, which give rises to a driving force to move the droplet towards the spindle-knot, given by:

(2)

Where is the surface tension of water; A and R are the advancing and receding angles of droplet on spider silk,
respectively; dl is the integrating variable along the length from joint (Lj) to spindle-knot (Lk).
Guided by insights into unique spindle-knot structure on spider silk, many bio-inspired fibers have been designed
and fabricated via various methods, as shown in Figure 1b-f. Among them, dip-coating is the most sophisticated way
[1, 15-24]. Depending on Rayleigh instability of polymer film along the main fiber, alternate PMMA-spindle-knot
(~47 m)/joints (~18 m) with periodicity of ~400 m can be generated in the drawing-out process (Figure 2b). The
SEM images also demonstrate a surface energy gradient between spindle-knot and joint, i.e., the pores are randomly
distributed on the spindle-knot, but stretched on the joint, which resembles the wettable gradient of spider silk.
Additionally, according to capillary number (Ca, in proportion to the thickness of coating film):

(3)
through adjusting some crucial parameters, including solution viscosity (), drawing velocity (V), and solution surface
tension (), the geometrical configuration of spindle-knotted fibers can be controlled regularly [16, 25, 26,]. Generally,
a high Ca value leads to a spindle-knot with large size. Importantly, based on dip-coating method, some modifying
ways can be applied to achieve various kinds of spindle-knots, such as with gradient- [27, 28] or multi-level sizes [18,
21], controlled micro-pores [23], tunable elasticity [29] and 3d helical cracks [20]. However, dip-coating is limited to
its small-scale preparation, thus in order to achieve a large scale fabrication, we developed fluid-coating [28, 30]
(Figure 1b) and coaxial-electrospinning strategies (Figure 1c) [31, 32] for continuously producing spindle-knotted
fibers. As to fluid-coating strategy, a fiber is guided by two capillary tubes to pass through a reservoir containing
coating solution. The fiber is steadily drawn out of the reservoir by a motor. Owing to the viscous force, the liquid
moves with the fiber, and relying on Raleigh instability, finally, the coating film breaks up into periodic droplets,
which becomes spindle-knots after solvent volatilization. As to coaxial-electrospinning, the electrospinning jet is
consisted of inside and outside channels (Figure 1c), which are fed with two different liquids, i.e., a dilute solution is
applied as outer fluid, which can be electrosprayed into micro-particles owing to Rayleigh instability, meanwhile a
viscous solution is chosen as the inner solution, which can be electrospun into micro/nano-fibers. The inner fiber acts
as support fiber and the outer fluid forms spindle-knots, then necklaced by the inner fiber, such as PMMA-knotted PS
fibers [32], and PEG-knotted PS fibers [31] (Figure 1c). Small diameter of electrospinning fibers (~200nm to ~2 m)
is favorable for collecting tiny droplets whose vapor pressure is higher than large ones [32]. Actually, the methods for
obtaining spindle-knots are not limited to Rayleigh instability, wet-assembly is also a delicate route for designing
spindle-knotted fibers [33, 34]. As illustrated in Figure 1e, due to large special surface area, an electrospinning fiber
easily absorbs nanoparticles. When the nanoparticles-covered fiber is placed in a humidity environment, tiny droplets
start to condense on the nanoparticles to form particle-in-droplets, which will coalesce with each other while their size

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grow big enough. Taking advantages of energy released from the coalescence of droplets, the particle-in-droplets selfassemble into periodic big ones. Finally, after water evaporation, spindle-knots are achieved successfully. Especially,
the nanoparticles can range from organic (PVDF, [33]) or inorganic materials (TiCl4 hydrolyzed nanoparticles (THN),
[34]), and a completely heterogeneous spindle-knot can be realized. As shown in Figure 1e, when on a THN
(spindle)/PMMA(knot) fibers, the elemental mapping indicates that THN(red) is distributed only in the spindle-knot
regions [34]. Another creative strategy, microfluidic technology, is inspired by the real silk-spinning process of natural
spiders, i.e., controllable multi-channel spinning [35]. As an example shown in Figure 1f, an alginate/salt solution is
introduced at a high feeding rate for forming a spindle-knot, while an alginate solution is at a low feeding rate for
forming main fiber. Meanwhile, via alternately opening/closing the valve operation, a porous spindle-knot/joint
structure is prepared after removing the salt component [36].Using microfluidic technology, the composition and
geometry size can be easily tailored.

Figure 1.Mimic nature spider silk. (a) wet-rebuilt of natural spider silk. Puffs are distributed along two main-axis fibers. The diameter of puff is
130.8 11.1 m, separated by joints (41.6 8.3 m in diameter) with a periodicity of ~85. 6 5.1 m. After absorbing water, original puffs deform
to spindle-knots (apex angles 19o, ~21.0 2.7 m), and the silk is composed of alternate spindle-knots and joints (~5.9 1.2 m) with a
periodicity of ~89.3 13.5 m. Due to spindle-knot/joint structure and roughness difference, a Laplace pressure difference and a wettable gradient
are formed on the spindle-knot. (b-e) various methods for obtaining artificial spindle-knotted fibers: (b) Dip-coating method. The as-prepared fibers
shows a size-controlled spindle-knot/joint structure and a roughness gradient, which are highly similar to that of nature spider silk. (c) Fluid-coating.
This fluid-coating apparatus can continuously coat the nylon fiber with polymer solution and produce the spindle-knotted fibers on a large scale.
(d) Coaxial-electrospinning. Via integrating electrospinning and electrospray techniques using a coaxial-jet, the micro-electrospray spheres are
necklaced by the electrospinning fibers to knit a large-scale spindle-knotted fibrous mat. (e) Wet-assembly. Using energy of droplet coalescence,

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the absorbed nano-particles can self-assemble to ordered spindle-knots. Nanoparticles can range from organic or inorganic materials, and a perfect
heterogeneous spindle-knot/joint can be obtained (f) Microfluidic technology. Inspired by real spinning process of nature spider, the geometry size
and chemical component of fibers can be flexibly tailored by operating open/close value and flow rate.

3. Applications of Spindle-knotted Fibers

Compared with uniform fibers, the fibers with spindle-knots have excellent water-collecting ability, including
directionality, strong hanging-droplet ability and high efficiency. As shown in Figure 2a, when on a PMMA-spindleknot (~500m and ~150 m in length and width, respectively), with a cooperation of surface energy gradient and
Laplace pressure force, as time increases, tiny droplets (~50 m in size) initially randomly condense around spindleknot. As size increases, the droplets start to coalesce directionally towards the middle of spindle-knot [30]. Whats
more, as a comparison with uniform fiber, the spindle-knot (see Figure 2a) can provide a longer and stable TCL (threephase contact line) in droplet-growing process [15, 17]. For a fiber with 47-m-height spindle-knots, as droplet volume
increases from ~3.2 L to ~4.2 L, the TCL stably remains around 405 m, while on a 50m uniform fiber, the TCL
decreases obviously from ~650 m to ~300 m, when droplet increases from ~2.0 L to ~3.3 L [17]. The combination
of directional water coalescence and excellent hanging ability results into a high water collection efficiency. It is
reported that the collection efficiency of a typical PMMA-spindle-knotted fiber (~18 m in diameter, 1.5 mm in length)
is about 200 nL/min when placed in a vertical fog flow (~75 cm/s) [16]. Besides, for a electrospinning PVDF spindleknotted fiber, the Vdroplet/Vfiber value (Vdroplet,max-volume of hanging droplet, Vfiber, volume of fiber) can reaches up to
~5.09 107, which is three orders of magnitude lager than natural spider (~5.21 10 4) [33]. Using size-gradient
spindle-knotted fibers, a long distance droplet transport becomes possible [28]. Figure 2b shows a line of increasingsize PMMA-spindle-knots. Depending on multi-forces, consisted of (1) a difference of Laplace pressure (Fl); (2)
capillary adhesion force (Fc); (3) energy released by the droplets coalescence, a 6.6-mm-droplet-tansport is achieved
on this fiber that the droplets grow in initial PMMA-spindle-knots and coalesce directionally form small spindle-knot
to big ones with a maximum volume of ~188.7 L in ~166.8s [28]. And so on, a concentrate and a departure longdistance droplet transport can be observed when on middle symmetric- or two-side symmetric size-gradient spindleknotted fibers, respectively.
Inspired by gradient cooperation, through introducing responsible component into the spindle-knots, a reversible
wettability is acquired via adjusting stimulus conditions. For a thermal-responsible PMMA-b-PNIPAAm spindle-knot
[22], when temperature below LCST (lower critical solution temperature, 25oC), the surface exhibits a hydrophilic
property (CA, 51.64o). Consequently, the droplets move towards the middle of knot. While temperature above LCST
(e.g., 40 oC), the surface of spindle-knots exhibits a hydrophobic property (CA, 107.09o), so water droplets move away
from spindle-knot. The similar situation is also observed on a photo-responsive P(MMA-Azo) spindle-knot [37]. The
spindle-knot can transform from a less hydrophilic to hydrophilic state after the Vis treatment, leading to a directionswitchable droplet movement. These studies are significant to design and fabricate smart materials which control the
motion droplets in different directions. Furthermore, Figure 2d shows that the PEG (spindle-knot)/PS (joint) fibers
possess an intelligent response to humidity change. With a change in humidity (from 55% to100%), the spindleknot exhibits a swelling behavior (size increases from ~7.2 mto ~9.5 m) whereas the joint remains the same
(~2.2m). These wet-responsible fibers are potentially applied as the water collection/release devices.

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Figure 2. Applications of spindle-knotted fibers. (a) Excellent water collection ability. A typical directional water collection on a PMMA-spindleknot (~500 m and ~150 m in length and width, respectively), with a cooperation of surface energy gradient and Laplace pressure force, as time
increases, tiny droplets (~50 m in size) coalesce directionally towards the spindle-knot. As compared with uniform fiber, spindle-knot can provide
a more sable TCL (~405 m) in the droplet growing process (from ~3.2 L to ~4.2 L). (b) Long distance droplet transport. A 6.6-mm-droplettansport is achieved on an increasing-size spindle-knotted fiber accompanied by droplets growing and coalescing directionally form small spindleknot to big ones with a maximum volume of ~188.7 L in ~166.8s. Besides, concentrate and departure droplet transport can be observed on twoside and middle symmetric gradient fibers, respectively. (c) Temperature or photo-responsive directional droplet movement. Through introducing
responsive component, spindle-knots exhibit a reversible wettability. The droplets can be manipulated reversibly in directions-towards or away
from spindle-knot-by adjusting the photo- or thermal-stimulus. (d) Wet-responsive PEG-knotted PS fibers. The micro-fibers, with alternate
hydrophilic (PEG) knots (~7.2 m) and hydrophobic (PS) joints (~2.2 m), show a smart response to environment change. As humidity increases,
hydrophilic region exhibits a swelling behavior whereas hydrophobic region remains the same.

4. Conclusion
Several methods have been developed to mimic the spindle-knot structure from natural evolution. Those artificial
fibers exhibit a unique directional wettable property. Actually, this research is just a beginning. More potential
applications are deserved to be explored and applied in many other realms, such as air filtration, sensor, micro-reactor,
drug delivery, etc.
Acknowledgements
This work is supported by National Research Fund for Fundamental Key Project (2013CB933001), National Natural

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701

Science Foundation of China (21234001, 21473007), Doctoral Fund of Ministry of Education of China
(20121102110035), and Graduate Student Innovation Practice Foundation of Beihang University.
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