The present invention is concerned with a superhydrophobic surface arrangement, an article comprising such arrangement, and a method of manufacture of thereof.
Engineering surfaces that promote rapid detachment of liquid drops are of importance to a wide range of applications including anti-icing, drop-wise condensation, and self-cleaning. The prior art has proposed superhydrophobic surface arrangements which may be able to allow some degree of drop detachment although they are not satisfactory. In the field of surface engineering, due to the numerous factors which could play into the surface there has been on-going challenges to provide specific surface arrangements which can yield a particular and effective liquid contact behavior.
The present invention seeks to provide a superhydrophobic surface arrangement with significantly improved drop detachment capability in that the particular surface arrangement can effect not pancake bouncing but also reduction of contact time, or at least to provide an alternative to the public.
According to a first aspect of the present invention, there is provided a superhydrophobic surface arrangement for generating, upon contact by water droplets, pancaking bouncing and reducing liquid contact time, comprising an array of posts residing on a surface and extending from the surface, the posts having an elongate configuration with a base portion at one end and an upper portion at an opposite end, wherein:
Preferably, the posts when having the straight post profile may be in the form of a square column, and the posts when having the conical profile may have a truncated profile with a substantially flat top.
According to a second aspect of the present invention, there is provided a substrate comprising a superhydrophobic arrangement as described above.
Preferably, the method may comprise steps of forming said posts by wire cutting and cyclic chemical etching.
Suitably, the posts may be formed from cooper.
Some embodiments of the present invention will now be explained, with reference to the accompanied drawings, in which:
In the field of superhydrophobic surface arrangements, there had been a constant challenge to provide a surface arrangement which can effect a reduced liquid contact time when liquid droplets (e.g. water droplets) engage the surface. For example, it had been difficult for scientists to provide a surface which can effect a pancake bouncing behavior and a reduced liquid contact time. Alternatively, liquid drops in contact with the surface tend spread to spread and stay with the surface. Alternatively, the liquid drops may only bounce away in a random manner but without firstly forming a pancake bouncing profile. In other instances, the liquid drops, regardless the physical profile thereof during bouncing, tend to require relatively long time before they can disengage from the surface.
The present invention is concerned with a superhydrophobic arrangement such as a superhydrophobic surface patterned with lattices of submillimetre-scale posts which, on engagement by liquid droplets (e.g. water droplets) would generate pancake bouncing of the droplets and reduce the contact time of the droplets after they have engaged the surface. During the course leading to the present invention, it was identified that a surface configuration contributed by a specific combination of surface parameters, upon engagement of liquid droplets, can generate a pancake bouncing behavior and a reduced contact time of the liquid droplets. The present invention allows for a substantially four-fold reduction in contact time compared to a conventional complete rebound. Conventional complete rebound referred herein are systems discussed in Richard et al 2002, Reyssat et al, Okumura et al 2003 and McCarthy et al 2012 in which the contact time in terms of C is substantially 2.6. Studies leading to the present invention show that with such arrangement the pancake bouncing results from the rectification of capillary energy stored in the penetrated liquid into upward motion adequate to lift the drop. With such configurations, the timescales become independent of the impact velocity, allowing the occurrence of pancake bouncing and rapid drop detachment over a wide range of impact velocities. The studies also show that while nano-textures may further improve the bouncing behavior, they are not necessary in the context of the present invention.
In one embodiment of the present invention, there is provided a copper surface arrangement patterned with a square lattice of tapered posts decorated with nanostructures. Please see
The post surface is fabricated using a wire cutting machine followed by chemical etching to generate the posts. After a thin polymer coating, trichloro(1H,1H,2H,2H-peruorooctyl)silane, is applied, the surface exhibits a superhydrophobic property with an apparent contact angle of over 165°. The advancing and receding contact angles are 167.2±1.1° and 163.9±1.4°, respectively. Water drop impact experiments were conducted using a high speed camera at the rate of 10,000 frames per second. The unperturbed radius of the drop is r0=1.45 mm or 1.10 mm, and the impact velocity (v0) ranges from 0.59 ms−1 to 1.72 ms−1, corresponding to 7.1<We<58.5, where We=ρv02r0/γ is the Weber number, with ρ the density and γ being the surface tension of water.
The difference in bouncing dynamics between conventional rebound and pancake bouncing can be quantified by the ratio of the diameter of the drop when it detaches from the surface djump to the maximum spreading width of the drop dmax. The ratio Q=djump/dmax is defined as the pancake quality, with Q>0.8 referred to as pancake bouncing. At low Weber number (We<12.6), the pancake quality Q is ˜0.4, corresponding to conventional bouncing. Please see
However, for We>12.6 there is a clear crossover to Q˜1, which corresponds to pancake bouncing. Moreover, a defining feature of pancake bouncing, of particular relevance to applications aimed at rapid drop shedding, is the short contact time of the drop with the solid surface. In the case of pancake bouncing, the contact time, tcontact, is reduced by a factor of over four to 3.4 ms as compared to conventional rebound.
Drop impact experiments were also performed on tilted surfaces which is more relevant geometrically to practical applications, such as self-cleaning, de-icing and thermal management.
These results indicate that the pancake bouncing of a drop occurring close to its maximum lateral extension results from the rectification of the capillary energy stored in the penetrated liquid into upward motion adequate to lift the entire drop. Moreover, for the drop to leave the surface in a pancake shape, the timescale for the vertical motion between posts should be comparable to that for the lateral spreading. In order to illustrate that pancake bouncing is driven by the upward motion rendered by the capillary emptying, comparison was made between the two timescales tcontact and t⬆, where t⬆ is the time interval between the moment when the drop first touches the surface and when the substrate is completely emptied, during which fluid undergoes the downward penetration and upward capillary emptying processes. As shown in
Comparison was made on the experimental results for bouncing on straight square posts covered by nanoflower structures. The post height and edge length (b) are 1.2 mm and 100 μm, respectively. It was observed that the pancake bouncing behavior is also affected by center-to-center post spacing and We. Pancake bouncing is absent on post arrays with center to center spacing w=200 μm, whereas it occurs for surfaces with w=300 μm and 400 μm.
Analysis was conducted to elucidate the enhanced pancake bouncing observed on tapered posts in comparison to straight posts. The timescale tmax scales as √{square root over (ρr03/γ)}, independent of the impact velocity. To calculate t⬆, the kinetics involved in the processes of liquid penetration and capillary emptying was considered. Here, the viscous dissipation was neglected since the Reynolds number in the impact process is ˜100. The liquid penetrating into the space between posts is subject to a capillary force, which serves to halt and then reverse the flow. The capillary force can be approximated by bnγ cos θγ, where n is the number of posts wetted, and θγ is the intrinsic contact angle of the nanoflower-covered posts. The deceleration (acceleration) of the penetrated liquid moving between the posts scales as a1˜bγ cos θγ/(ρr0w2), where the drop mass ˜ρr03, n˜r02/w2, and it is considered that the liquid does not touch the base of the surface. It is to be noted that the number of posts wetted is independent of We because the penetrating liquid is mainly localized in a region with a lateral extension approximatively equivalent to the initial drop diameter, rather than the maximum spreading diameter. For straight posts, the acceleration is constant. Thus, t1˜v0/a1˜v0ρr0w2/(−bγ cos θγ), and the ratio of the two timescales can be expressed as
which scales as √{square root over (We)}. These experiments show, and as discussed previously, that the occurrence of pancake bouncing requires t- and tmax to be comparable, i.e., k˜1. The dependence of k on We indicates that this condition can be satisfied only over a limited range of We.
Unexpectedly, k and We become decoupled by designing surfaces with tapered posts. Since the post diameter b now increases linearly with the depth z below the surface (that is, b˜βz, where β is a structural parameter), the acceleration of the penetrated liquid moving between posts is linearly proportional to penetration depth (i.e., a↑∝z). As a result, the surface with tapered posts acts as a harmonic spring with t↑∞√{square root over (w2r0ρ/(−βγ cos θγ))}. Therefore, the ratio of timescales becomes
which is independent of We.
To pin down and demonstrate the key surface features and drop parameters for the occurrence of pancake bouncing, we plotted the variation of k with √{square root over (We)} in the design diagram. Please see
Filled symbols represent pancake bouncing (defined by Q>0.8) and open symbols denote conventional bouncing. Region 1 corresponds to the pancake bouncing occurring on straight posts with 1.0<k<1.7. The data show that k˜√{square root over (We)} as predicted by equation (1) above. Such a dependence of k on We explains the limited range of We for which such rebound is observed in the experiments. The two slanting lines bounding Region 1 for pancake bouncing on straight posts correspond to w2/(−br0 casθγ)=0.45 and 1.5 in equation (1). For almost all the reported, this parameter takes values between 0.01 and 0.144, smaller than the threshold demonstrated in the studies leading to the present invention by at least one order of magnitude. On such surfaces, either the liquid penetration is insignificant (for example, owing to too narrow and/or too short posts) or the capillary energy stored cannot be rectified into upward motion adequate to lift the drop (for example, owing to an unwanted Cassie-to-Wenzel transition). Region 2 shows that the introduction of tapered posts significantly widens the range of timescale and Weber number for pancake bouncing, way beyond Region 1. In this Region, the pancake bouncing can occur over a wider range of k from 0.5 to 1.7 and We from 8.0 to 58.5. As illustrated above, for small We with moderate liquid penetration, the two timescales tmax and t⬆ are independent of We. They become weakly dependent on We for relative large We due to the penetrated liquid hitting the base of the surface, but the emergence of pancake bouncing is rather insensitive to the post height as long as this is sufficient to allow for adequate capillary energy storage. For much shorter posts, for example the tapered surface with a post height of 0.3 mm, there was no observation of pancake bouncing due to insufficient energy storage.
The novel pancake bouncing is also observed on a multi-layered, two-tier, superhydrophobic porous (MTS) surface. The top layer of the MTS surface consists of a post array with post centre-to-centre spacing of ˜260 μm and the underlying layers comprise a porous medium of pore size 200 μm, naturally forming a graded pathway for drop penetration and capillary emptying. The typical contact time of the drop with the MTS surface is tcontact˜5.0 ms and the range of We is between 12 and 35 for pancake bouncing. These values are comparable to those on tapered surfaces. Taken together, it is shown that tapered post surfaces and MTS surfaces of the present invention demonstrate the counter-intuitive pancake bouncing and is a general and robust phenomenon. Moreover, there is enormous scope for designing structures to optimize pancake bouncing for multifunctional applications.
Methods
Preparation of Tapered Surface and Straight Post Arrays
The tapered surface with a size of 2.0×2.0 cm2 was created based on type 101 copper plate with a thickness of 3.18 mm by combining a wire-cutting method and multiple chemical etching cycles. Square posts in the configuration of square prisms arranged in a square lattice were first cut with a post centre-to-centre spacing of 200 μm. The post edge length and height are 100 μm and 800 μm, respectively. Then the as-fabricated surface was ultrasonically cleaned in ethanol and deionized water for 10 min, respectively, followed by washing with diluted hydrochloric acid (1 M) for 10 s to remove the native oxide layer. To achieve a tapered surface with post diameter of 20 μm at the top, six cycles of etching were conducted. In each cycle, the as-fabricated surface was first immersed in a freshly mixed aqueous solution of 2.5 moll−1 sodium hydroxide and 0.1 mll−1 ammonium persulphate at room temperature for ˜60 mins, followed by thorough rinsing with deionized water and drying in nitrogen stream. As a result of chemical etching, CuO nanoflowers with an average diameter ˜3.0 μm were produced. Note that the etching rate at the top of the posts is roughly eight-fold of that at the bottom of the surface due to the formation of an etchant solution concentration gradient generated by the restricted spacing between the posts. To facilitate further etching, after each etching cycle the newly-etched surface was washed by diluted hydrochloric acid (1 M) for 10 s to remove the oxide layer formed during the former etching cycle. Then another etching cycle was performed to sharpen the posts. In preparing the straight post arrays, only one etching cycle was conducted. All the surfaces were modified by silanzation through immersion in 1 mM n-hexane solution of trichloro(1H,1H,2H,2H-peruorooctyl)silane for ˜60 mins, followed by heat treatment at −150° C. in air for 1 hour to render surfaces superhydrophobic.
Preparation of MTS Surface
The MTS surface is fabricated on a copper foam with density 0.45 gcm−3, porosity 94%, and thickness 0.16 cm. The nanostructure formation on the MTS surface and silanization were conducted using the same procedures described above.
Contact Angle Measurements
The static contact angle on the as-prepared substrate was measured from sessile water drops with a ramé-hart M200 Standard Contact Angle Goniometer. Deionized water drops of 4.2 μl, at room temperature with 60% relative humidity, were deposited at a volume rate of 0.5 l s−1. The apparent, advancing (θa) and receding contact angles (θr) on the tapered surface with centre-to-centre spacing of 200 μm are 165.6±1.3°, 167.2°±1.1° and 163.9°±1.4°, respectively. The apparent (equivalent to the intrinsic contact angle on a tapered surface), advancing (θa) and receding contact angle (Or) on the surface with nanoflower structure alone are 160°±1.8°, 162.4°±2.8°, and 158.8°±1.7°, respectively. At least five individual measurements were performed on each substrate.
Impact Experiments
The whole experimental setup was placed in ambient environment, at room temperature with 60% relative humidity. Water drops of −13 μl and 6 μl (corresponding to radii ˜1.45 mm and 1.10 mm, respectively) were generated from a fine needle equipped with a syringe pump (KD Scientific Inc.) from pre-determined heights. The dynamics of drop impact was recorded by a high speed camera (Fastcam SA4, Photron limited) at the frame rate of 10,000 fps with a shutter speed 1/93,000 sec, and the deformation of drops during impingement were recorded using Image J software (Version 1.46, National Institutes of Health, Bethesda, Md.).
It should be understood that certain features of the invention, which are, for clarity, described in the content of separate embodiments, may be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the content of a single embodiment, may be provided separately or in any appropriate sub-combinations. It is to be noted that certain features of the embodiments are illustrated by way of non-limiting examples. Also, a skilled person in the art will be aware of the prior art which is not explained in the above for brevity purpose. For example, a skilled in the art is aware of the prior art listed below. Contents of this prior art are incorporated herein in their entirety.
The present invention is a continuation-in-part from U.S. patent application Ser. No. 14/606,105 filed on Jan. 27, 2015, the entire disclosure of which is incorporated herein by reference.
Number | Name | Date | Kind |
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20070224391 | Krupenkin et al. | Sep 2007 | A1 |
20160214152 | Wang et al. | Jul 2016 | A1 |
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103640278 | Mar 2014 | CN |
Entry |
---|
Denis Richard et al., Contact Time of a Bouncing Drop, Nature Publishing Group, vol. 417, Jun. 20, 2002. |
James C. Bird et al., Reducing the Contact Time of a Bouncing Drop, Macmillan Publishers Limited, vol. 503, Nature, Nov. 21, 2013. |
Stefan Jung et al., Mechanism of Supercooled Droplet Freezing on Surfaces, Nature Communications, published Jan. 10, 2012. |
Lidiya Mishchenko et al., Design of Ice-Free Nanostructured Surfaces Based on Repulsion of Impacting Water Droplets, ACSNANO, vol. 4, No. 12, 2010. |
Howard A. Stone, Ice-Phobic Surfaces that are Wet, ACSNANO, vol. 6, No. 8, 2012. |
Xuemei Chen et al., Nanograssed Micropyramidal Architectures for Continuous Dropwise Condensation, Advanced Functional Materials, 2011. |
Ralf Blossey, Self-Cleaning Surfaces-Virtual Realities, Nature Materials, vol. 2, May 2003. |
Anish Tuteja et al., Designing Superoleophobic Surfaces, Science Mag, vol. 318, Dec. 7, 2007. |
Xu Deng et al., Candle Soot as a Template for a Transparent Robust Superamphiphobic Coating, Science Mag, vol. 335, Jan. 6, 2012. |
K. Okumura et al., Water Spring: A Model for Bouncing Drops, Europhysics Letters, 62 (2), Apr. 15, 2003. |
M. Reyssat et al., Bouncing Transitions on Microtextured Materials, Europhysics Letters, 74 (2), Apr. 15, 2006. |
D. Bartolo et al., Bouncing or Sticky Droplets: Impalement Transitions on Superhydrophobic Micropattemed Surfaces, Europhysics Letters, 74 (2), Apr. 15, 2006. |
Matthew McCarthy et al., Biotemplated Hierarchical Surfaces and the Role of Dual Length Scales on the Repellency of Impacting Droplets, Applied Physics Letters, 100, 2012. |
S. Moulinet et al., Life and Death of a Fakir Droplet: Impalement Transitions on Superhydrophobic Surfaces, The European Physical Journal E, 24, 2007. |
Yong Chae Jung et al., Dynamic Effects of Bouncing Water Droplets on Superhydrophobic Surfaces, Langmuir, 2008. |
Tae-Gon Cha et al., Nanoscale Patterning of Microtextured Surfaces to Control Superhydrophobic Robustness, Langmuir Article, published Feb. 12, 2010. |
Tuan Tran et al., Droplet Impact on Superheated Micro-Structured Surfaces, Soft Matter, RSC Publishing, 2013. |
Xinhua Chen et al., Synthesis and Characterization of Superhydrophobic Functionalized Cu(OH)2 Nanotube Arrays on Copper Foil, Applied Surface Science, 2009. |
Chrisophe Clanet et al., Maximal Deformation of an Impacting Drop, J. Fluid Mech. vol. 517, 2004. |
Ivan U. Vakarelski et al., Stabilization of Leidenfrost Vapour Layer by Textured Superhydrophobic Surfaces, Nature, vol. 489, Sep. 13, 2012. |
Andreas N. Lembach et al., Drop Impact, Spreading, Splashing, and Penetration into Electrospun Nanofiber Mats, Langmuir Article, Mar. 5, 2010. |
Xu Deng et al., Liquid Drops Impacting Superamphiphobic Coatings, Langmuir Article, May 22, 2013. |
Lei Xu et al., Drop Splashing on a Dry Smooth Surface, Physical Review Letters, May 2013. |
Robert N. Wenzel, Resistance of Solid Surfaces to Wetting by Water, Industrial and Engineering Chemistry, vol. 28, No. 8, Mar. 27, 1936. |
A. B. D. Cassie et al., Wettability of Porus Surfaces, RSC Org, published Jan. 1, 1944. |
Aurelie Lafuma et al., Superhydrophobic States, Nature Materials, vol. 2, Jul. 2003. |
Tuukka Verho et al., Reversible Switching Between Superhydrophobic States on a Hierarchically Structured Surface, PNAS vol. 109, No. 26, Jun. 26, 2012. |
A.L. Yarin, Drop Impact Dynamics: Splashing, Spreading, Receding, Bouncing . . . , Annu. Rev. Fluid Mech. 2006. |
David Quere, Wetting and Roughness, Annu. Rev. Mater. Res. 2008. |
Yongmei Zheng et al., Directional Water Collection on Wetted Spider Silk, Nature Letters, vol. 463, Feb. 4, 2010. |
Shirtcliffe et al., “Wetting and Wetting Transitions on Copper-Based Super-Hydrophobic Surfaces,” Jan. 7, 2005, Langmuir, American Chemical Society, Issue 21, pp. 937-943. |
Office Action in U.S. Appl. No. 14/606,105, filed Oct. 18, 2016, 50 pgs. |
Final Office Action in U.S. Appl. No. 14/606,105, filed Jun. 15, 2017, 20 pgs. |
Office Action in U.S. Appl. No. 14/606,105, filed Mar. 7, 2018, 16 pgs. |
Final Office Action in U.S. Appl. No. 14/606,105, filed Oct. 1, 2018, 16 pgs. |
Number | Date | Country | |
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20190127856 A1 | May 2019 | US |
Number | Date | Country | |
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Parent | 14606105 | Jan 2015 | US |
Child | 16233325 | US |