Switchable liquid repellent and active water harvesting surface
10730789 ยท 2020-08-04
Assignee
Inventors
- Tak-Sing Wong (University Park, PA, US)
- Yu Huang (University Park, PA, US)
- Birgitt BOSCHITSCH (University Park, PA, US)
- Nan SUN (University Park, PA, US)
Cpc classification
C03C17/3405
CHEMISTRY; METALLURGY
C09D5/1681
CHEMISTRY; METALLURGY
C03C17/42
CHEMISTRY; METALLURGY
International classification
C03C17/34
CHEMISTRY; METALLURGY
C03C17/42
CHEMISTRY; METALLURGY
Abstract
A substrate with a switchable surface has been developed that can rapidly switch its surface character such as between two distinct liquid-repellent modes: (1) a superhydrophobic mode and (2) a slippery mode. Such surfaces have demonstrated adaptive liquid repellency and water harvesting capabilities.
Claims
1. A substrate with a switchable surface, comprising: an array of magnetically responsive micropillars, each of the micropillars including a flexible polymer and a magnetically responsive particle; and a lubricant layer conformally infused onto the micropillars, wherein the micropillars have a first orientation predominately upright relative to the surface corresponding to a superhydrophobic state of the switchable surface and a second orientation angled relative to the first orientation corresponding to a slippery state of the switchable surface.
2. The substrate according to claim 1, wherein the magnetically responsive micropillars are hierarchical micropillars having self-assembling nanoparticles forming a textured surface on the micropillars.
3. The substrate of claim 1, wherein the magnetically responsive particle is an iron microsphere.
4. The substrate of claim 1, wherein the flexible polymer comprises polydimethylsiloxane.
5. The substrate of claim 1, wherein the lubricant comprises a perfluorinated oil, a silicone oil, a polydimethylsiloxane, a hydroxy polydimethylsiloxane or any combination thereof.
6. A method of switching a surface character of a substrate with a switchable surface, the method comprising the step of: providing a substrate with a switchable surface, including: an array of magnetically responsive micropillars, each of the micropillars including a flexible polymer and a magnetically responsive particle; and a lubricant layer conformally infused onto the micropillars, wherein the array of micropillars has a first orientation predominately upright relative to the surface corresponding to a superhydrophobic state of the switchable surface and a second orientation angled relative to the first orientation corresponding to a slippery state of the switchable surface; and applying an external magnetic field to the substrate, thereby changing the orientation of the array between the first and second orientations and causing the switching of the surface between the superhydrophobic and slippery states.
7. The method of claim 6, comprising orienting the array predominately parallel relative to the substrate.
8. The method of claim 6, comprising repeatedly changing the orientation of the array.
9. A water harvesting device comprising a substrate of claim 1.
10. The method of claim 6, comprising orienting the array predominately perpendicular relative to the substrate.
11. The method according to claim 6, further comprising the step of restoring the superhydrophobic state by first switching the surface to the slippery state to remove pinned water droplets.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Reference is made to the attached drawings, wherein elements having the same reference numeral designations represent similar elements throughout and wherein:
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DETAILED DESCRIPTION OF THE DISCLOSURE
(8) Here, we designed a magnetically transformable surface that can reversibly switch between the lotus and the pitcher plant mode. That is, we have shown that the surface can form air-infused textures to repel impinging liquid droplets in a manner similar to that of a lotus leaf, and can be reversibly transformed into a liquid-infused textured surface to maintain a highly slippery interface akin to the peristome of a pitcher plant.
(9) By switching the liquid-repellent state on-demand, our transformable surface maintains high droplet mobility in the lotus mode and can retain its liquid-repellent function under high pressure conditions in the pitcher plant mode. We have demonstrated that the transformable surface can be used for adaptive liquid repellency and programmable fluid collection and transport. The ability to dynamically alter liquid-repellent properties on-demand allows for smart liquid-repellent skin, programmable fluid collection and transport, adaptive drag control, thermal regulation, and controlled-release devices.
(10) In an aspect of the present disclosure, a magnetically transformable surface that can switch between a superhydrophobic state and a slippery state is provided. In an embodiment of the present disclosure, a substrate with a switchable surface can include an array of magnetically responsive hierarchical micropillars and a lubricant layer conformally infused on the micropillars. Advantageously, each of the micropillars comprises a magnetically responsive particle and a flexible polymer.
(11) The orientations of the lubricated micropillars can be controlled by the direction of external magnetic fields. In the superhydrophobic state, the micropillars are oriented predominately vertically (i.e., predominately perpendicular relative to the substrate) so that a liquid droplet predominately touches the tips of the hydrophobic micropillars. In the slippery state, the micropillars predominately lay flat against the substrate (i.e., predominately parallel relative to the substrate), where an impacting droplet touches a nearly continuous film of lubricant-infused surface (see
(12) To switch the surface character of a substrate, e.g., create both the superhydrophobic and slippery states within a surface, both the geometrical parameters and the mechanical properties of the micropillars should be appropriately designed. Specifically, soft polymeric micropillars are used to allow for complete bending under the magnetic field to create the slippery state. Additionally, these pillars should be rigid enough to withstand the drop impact in the superhydrophobic state.
(13) To maintain the superhydrophobic state, the micropillars can be designed to prevent the impacting droplets from transitioning from the Cassie state (i.e., droplet on a stable air-layer) to the Wenzel state (i.e., droplet is fully impregnated into the textures). With this in mind, the micropillars were designed to meet three criteria: I) the Cassie state is the preferable state; II) the surface exhibits high pressure stability, and III) individual pillars are rigid enough to prevent buckling upon drop impact (Supplementary Information).
(14) To satisfy criteria (I), the intrinsic contact angle of the material, , has to be larger than .sub.c, the critical angle below which Cassie-to-Wenzel transition is favorable,
cos .sub.c=(.sub.s1)/(R.sub.s)(1)
(15) where .sub.s is the solid fraction and R is the roughness, defined as the ratio between real surface area and the projected surface area. For example, a surface consisting of cylindrical pillars of height h, interpillar spacing L, and diameter w arranged in square packing (we model our microtextures as regularly spaced cylinders for simplicity; in reality our textures are conical-like and randomly spaced), the solid fraction and the roughness can be expressed by
(16)
respectively. To further prevent the Cassie-to-Wenzel transition for the impinging droplets and satisfy criteria (II), the maximum pressure difference across the liquid-plastron interface before wetting occurs (P.sub.max) should exceed the dynamic pressure of the droplet (P.sub.d=V.sup.2).sup.[12],
(17)
(18) where , V, and are, respectively, the density, velocity impact, and surface tension of the droplet, and .sub.A is the advancing contact angle.
(19) To satisfy criteria (III), the critical buckling stress (P.sub.B) of the micropillar arrays have to sustain the dynamic pressure of the droplets in order to maintain the superhydrophobic state. It can be shown that P.sub.8 can be expressed as (Supplementary Information),
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(21) where I is the second moment of inertia of the pillar cross-section, and A.sub.pillar and E are the cross sectional area and Young's Modulus of the pillar, respectively.
(22) Since P.sub.max and P.sub.3 can be expressed as functions of pillar geometries and mechanical properties, one can engineer a transformable surface according to the drop impact environment. As an order of magnitude comparison, one can show that for fixed pillar geometries and arrangements, P.sub.max<<P.sub.B for microtextured surface made out of hard material (i.e., EGPa). Therefore, Eq. (2) will be the more critical design criteria. For soft material (i.e., E100 kPa), one can show that P.sub.max>>P.sub.B and Eq. (3) will determine the Cassie-to-Wenzel transition. Note that in our analysis, P.sub.B is a function of E while P.sub.max is not.
(23) Examples of useful materials that can be used for micropillars of the present disclosure include, for example, elastomers such as silicones, fluorosilicones, fluoroelastomers, perfluoroelastomers, or thermoplastics such as polyethylene, polypropylene, polycarbonate, poly(methyl methacrylate), polytetrafluoroethylene, or thermosetting polymers such as polyurethanes, epoxy resins, and any combination thereof. An array of micropillars can be formed by polymerizing a composition including a polymer forming ingredient, a curing agent, and magnetically responsive particles. The polymer forming ingredients are monomers that form the polymeric materials described above for micropillar materials, such as dimethylsiloxane, methyl methacrylate, propylene, ethylene, tetrafluoroethylene, etc. Magnetically responsive particles include, for example, magnetic metal particle such as a particle of iron, or iron oxide, etc. The particles can be in any form such as spheres, microspheres, etc. the particles can be in the composition at a weight ratio of from about 10 wt % to about 90 wt %, such as between about 50 wt % to about 85 wt %.
(24) Advantageously, the micropillars have a textured surface such as a nonstructured surface to facility retention of lubricant thereon.
(25) Examples of useful lubricants that can be used to infuse the micropillars include, for example, perfluorinated oils, silicone oils, polydimethysiloxane, hydroxy polydimethylsiloxane, mineral oil, plant oils, and any combination thereof.
(26) In an embodiment of the present disclosure, an array of magnetically responsive hierarchical micropillars can be fabricated from a mixture of polymerizable materials with magnetically responsive particles on a surface of a substrate.
(27) For example, to fabricate a magnetically transformable surface, we first mixed polymer forming ingredients, e.g., a polydimethylsiloxane (PDMS) pre-polymer (contained 5% equivalent curing agents), and magnetically responsive particles, e.g., carbonyl iron microspheres. The mixture is then coated onto a substrate, for this experiment, a glass substrate, to form a magnetically responsive layer (
(28) Once the magnetic micropillars were formed, we introduced nanoparticles onto these micropillars to form hierarchical structures. To form the nanostructures, the micropillars were first made hydrophilic through oxygen plasma treatment so that nanoparticles, e.g., polystyrene (PS) with diameter 200 nm, could self-assemble on the micropillars and the substrate. The resulting nanotextured micropillars help to retain a thin layer of lubricant onto the nanotextures only due to the dominance of capillary force. The sample was then silanized with a perfluorinated silane and coated with a layer of lubricant (e.g., perfluorinated oils, DuPont Krytox GPL 100) through a spin-coating process.
(29) Before the lubrication, the substrate is rough at the nanoscale due to the presence of the nanoparticles on the surface of micropillars. After applying lubricant, the surface is smooth at the nanoscale as the nanoparticle assembled layer is submerged beneath the liquid lubricant. A high resolution electron micrograph shows the uniform surface morphology of the micropillars (
(30) The geometries and the mechanical properties of the micropillar array can be tuned by adjusting the concentrations of magnetic microparticies (
(31) To demonstrate that our transformable surface can exhibit both superhydrophobic and slippery properties and can switch between these two states, we have carried out static and dynamic wetting characterizations. The results are shown in
(32) In the static experiments, we found that when the micropillars are in the vertical direction, a water droplet sitting on any of our surfaces was in the Cassie state; the droplet exhibited very high static contact angle (CA) (i.e., >150) with low contact angle hysteresis, and could roll off the surface at small tilting angles (<5), as shown in
(33) In an aspect of the present disclosure, the surface character of a substrate, which includes an array of magnetically responsive hierarchical micropillars and a lubricant layer conformally infused thereon, can be switched by changing the orientation of the array of micropillars with an external magnetic field. For example, by applying external magnetic field (from a RdFeB magnet, >0.1 T) at various angles, the micropillars shifted their orientations and can be in contact with adjacent micropillars to form a relatively flat surface, as verified by our observations through an optical microscope (see
(34) We systematically characterized the average droplet removal velocity on the transformable surface in both the superhydrophobic and slippery states under different We (
(35) The ability to quickly and repeatedly switch between superhydrophobic and slippery states will allow the maintenance of liquid repellency in fast changing dynamic environmental conditions. Therefore, we further characterized our surfaces by measuring the response time of the mechanical switching of the transformable surface with respect to the applied magnetic field. To test the mechanical response time, we applied a magnetic field using an electromagnet applied at a specific frequency (i.e., 10 Hz), and used a high speed camera to observe the mechanical switching behaviors of the transformable surface.
(36) We estimated that the time for the full magnetic field establishment for the electromagnet is 0.015 sec based on measured resistance and inductance of the electromagnet (Supplementary Information). We also measured the time required for individual micropillars to change from a predominately perpendicular (e.g., up-right) position relative to the substrate to a predominately parallel (e.g., nearly flattened) position based on the images obtained from a high speed camera. Based on our measurements, the typical mechanical switching time of the sample prepared with 66.7 wt % iron microspheres concentration is 0.020 sec, as shown in
(37) An advantageous function of our transformable surface is its ability to restore its liquid repellent function even when water droplets are pinned onto the surface. To illustrate this advantage, we conducted the following test. While our surface was in the superhydrophobic state, we dropped water droplets at a relatively high Weber number (i.e., We>7), such that the water droplet becomes completely impregnated into the surface textures, rendering the droplet immobile (i.e., failure mode of the superhydrophobic surface). To restore the liquid repellent function, we applied an external magnetic field to change the orientation of the micropillars from up-right to nearly flat morphology (i.e., slippery state). The change of the surface morphology resulted in the depinning and sliding of the liquid droplet, thereby restoring the liquid repellent function.
(38)
(39) This demonstration illustrates that our transformable surface can address the failure mode of superhydrophobic surface by first switching the surface to the slippery mode to remove the pinned water droplet, and switching back to (and thus restoring) the superhydrophobic mode. Such a precise control allows the transformable surface to be used as an adaptive liquid repellent system. To achieve high droplet mobility, one can adopt the superhydrophohic mode; to repel liquid droplets under pressure, for example, the slippery mode can be activated to retain its liquid repellency.
(40) In addition to the adaptive liquid repellent system, the transformable surface can be used with programmable fog harvesting (
Examples
(41) The following examples are intended to further illustrate certain preferred embodiments of the invention and are not limiting in nature. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein.
(42) Preparation of magnetically transformable surface: The micropillar arrays of the transformable surface were fabricated using a magnetic particle-assisted molding process. In this process, PDMS pre-polymer (containing 5 wt % curing agents; purchased from Dow Corning, SYLGARD 184) and carbonyl iron microspheres (purchased from chemicalstore.com, with diameter of 3 to 10 microns) with various weight ratios were mixed thoroughly using a planetary centrifugal mixer (Thinky, USA). The mixture was then coated onto a cover glass slide. By placing a permanent magnet (with a magnetic flux density 4 T) underneath the substrate, uniform and ordered micropillar arrays were firmed along the magnetic field direction. These micropillar arrays were left in the magnetic field at room temperature for 24 hrs for the complete curing of the final mixture. They were then treated with oxygen plasma to create a hydrophilic surface. 10 L of polystyrene nanoparticles suspension with a concentration of 0.15 wt % was deposited onto the micropillar arrays. The substrate was kept at room temperature for 10 min so that the nanoparticles could self-assemble by solvent evaporation. The thickness of the assembly can be controlled by repeating the process several times. The hierarchical micropillar arrays were silanized using 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (Sigma-Aldrich) inside a vacuum chamber for 4 hrs. After the silanization step, a perfluorinated lubricant (e.g., DuPont Krytox oils) was coated onto the silanized micropillars using a spin-coater spinning at around 500 RPM for several seconds.
(43) Drop impact experiments: In our experiments, surfaces with micropillar arrays were placed at a tilted angle of 25. We adjusted the release height of the water droplet in order to change We. Deionized water droplets of 10 L were dispensed from a syringe (Hamilton) at specific heights. The radius, R, and the droplet velocity, V, and release height h, were measured from a high speed camera (Phantom Miro M320S). Specifically, h was determined from the center of mass of the droplet using the Phantom Camera Control Application software. The diameter of the water droplet is 1.25 mm with a volume of 10 L. The droplet impact dynamics were recorded from the side view using the high-speed video camera with a typical frame rate of 1700 fps.
(44) The present disclosure describes and demonstrates a substrate with a switchable surface that can switch between and display interfacial functions attributed to individual biological species selectively by transforming the surface morphologies. While this work focuses on liquid-repellent materials, it can be extended to other interfacial functions such as adhesion and optical properties derived from multiple biological species as many of these natural interfacial functions are enabled by the micro/nanoscale surface textures. The ability to control interfacial properties on-demand allow for a new class of programmable interfacial materials with applications including adaptive skin friction and adhesion control, dynamic flow control, camouflage, and thermal regulation.
(45) Only the preferred embodiment of the present invention and examples of its versatility are shown and described in the present disclosure. It is to be understood that the present invention is capable of use in various other combinations and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein. Thus, for example, those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances, procedures and arrangements described herein. Such equivalents are considered to be within the scope of this invention, and are covered by the following claims.