Apparatus and methods employing liquid-impregnated surfaces

Abstract

In certain embodiments, the invention is directed to apparatus comprising a liquid-impregnated surface, said surface comprising an impregnating liquid and a matrix of solid features spaced sufficiently close to stably contain the impregnating liquid therebetween or therewithin, and methods thereof. In some embodiments, one or both of the following holds: (i) 0<ϕ≤0.25, where ϕ is a representative fraction of the projected surface area of the liquid-impregnated surface corresponding to non-submerged solid at equilibrium; and (ii) S.sub.ow(a)<0, where S.sub.ow(a) is spreading coefficient, defined as γ.sub.wa−γ.sub.wo−γ.sub.oa, where γ is the interfacial tension between the two phases designated by subscripts w, a, and o, where w is water, a is air, and o is the impregnating liquid.

Claims

1. An article comprising a liquid-impregnated surface, said surface comprising an impregnating liquid and a matrix of solid features spaced sufficiently close to stably contain the impregnating liquid therebetween or therewithin, wherein one or both of the following holds: (i) 0<ϕ≤0.25, where ϕ is a representative fraction of the projected surface area of the liquid-impregnated surface corresponding to non-submerged solid at equilibrium; and (ii) S.sub.ow(a)<0, where S.sub.ow(a) is spreading coefficient, defined as γ.sub.wa−γ.sub.wo−γ.sub.oa, where γ is the interfacial tension between the two phases designated by subscripts w, a, and o, where w is water, a is air, and o is the impregnating liquid, wherein the liquid-impregnated surface is non-wetting to a contacting liquid.

2. The article of claim 1, wherein 0.001<ϕ≤0.25.

3. The article of claim 1, wherein 0.001<ϕ≤0.10.

4. The article of claim 1, wherein S.sub.ow(a)<0.

5. The article of claim 1, wherein the impregnating liquid comprises an ionic liquid.

6. The article of claim 1, wherein the impregnating liquid comprises at least one member selected from the group consisting of tetrachloroethylene (perchloroethylene), phenyl isothiocyanate (phenyl mustard oil), bromobenzene, iodobenzene, o-bromotoluene, alpha-chloronaphthalene, alpha-bromonaphthalene, acetylene tetrabromide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIm), tribromohydrin (1,2,3-tribromopropane), ethylene dibromide, carbon disulfide, bromoform, methylene iodide (diiodomethane), stanolax, Squibb's liquid petrolatum, p-bromotoluene, monobromobenzene, perchloroethylene, carbon disulfide, phenyl mustard oil, monoiodobenzene, alpha-monochloro-naphthalene, acetylene tetrabromide, aniline, butyl alcohol, isoamyl alcohol, n-heptyl alcohol, cresol, oleic acid, linoleic acid, and amyl phthalate.

7. The article of claim 1, wherein the solid features comprise at least one member selected from the group consisting of a polymeric solid, a ceramic solid, a fluorinated solid, an intermetallic solid, and a composite solid.

8. The article of claim 1, wherein the solid features comprise a chemically modified surface, a coated surface, and/or a surface with a bonded monolayer.

9. The article of claim 1, wherein the solid features define at least one member selected from the group consisting of pores, cavities, wells, interconnected pores, and interconnected cavities.

10. The article of claim 1, wherein the solid features comprise at least one member selected from the group consisting of posts, nanoneedles, nanograss, substantially spherical particles, and amorphous particles.

11. The article of claim 1, wherein the solid features have a roughened surface.

12. The article of claim 1, wherein 0<ϕ≤0.25.

13. The article of claim 12, wherein 0<ϕ≤0.10.

14. The article of claim 1, wherein the liquid-impregnated surface is configured such that water droplets contacting the surface are not pinned or impaled on the surface and have a roll-off angle α of less than 40°.

15. The article of claim 14, wherein the water droplets have a roll-off angle α of less than 25°.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The objects and features of the invention can be better understood with reference to the drawing described below, and the claims.

(2) FIG. 1 illustrates a schematic cross-sectional and corresponding top view of a liquid-impregnated surface that are partially submerged.

(3) FIG. 2 includes a plot of roll-off angle versus emerged area fraction ϕ and two SEM images of BMIm impregnated texture, in accordance with certain embodiments of the invention.

(4) FIG. 3 and FIG. 4 demonstrate condensation inhibition by preventing coalescence due to liquid cloaking, in accordance with certain embodiments of the invention.

(5) FIG. 5 demonstrates condensation inhibition by less nucleation on high viscosity liquids, in accordance with certain embodiments of the invention.

(6) FIG. 6 demonstrates frost inhibition by less nucleation on high viscosity liquids, in accordance with certain embodiments of the invention.

DESCRIPTION

(7) It is contemplated that compositions, mixtures, systems, devices, methods, and processes of the claimed invention encompass variations and adaptations developed using information from the embodiments described herein. Adaptation and/or modification of the compositions, mixtures, systems, devices, methods, and processes described herein may be performed by those of ordinary skill in the relevant art.

(8) Throughout the description, where articles, devices, apparatus and systems are described as having, including, or comprising specific components, or where processes and methods are described as having, including, or comprising specific steps, it is contemplated that, additionally, there are articles, devices, apparatus and systems of the present invention that consist essentially of, or consist of, the recited components, and that there are processes and methods according to the present invention that consist essentially of, or consist of, the recited processing steps.

(9) Similarly, where articles, devices, mixtures, apparatus and compositions are described as having, including, or comprising specific compounds and/or materials, it is contemplated that, additionally, there are articles, devices, mixtures, apparatus and compositions of the present invention that consist essentially of, or consist of, the recited compounds and/or materials.

(10) It should be understood that the order of steps or order for performing certain actions is immaterial so long as the invention remains operable. Moreover, two or more steps or actions may be conducted simultaneously.

(11) The mention herein of any publication, for example, in the Background section, is not an admission that the publication serves as prior art with respect to any of the claims presented herein. The Background section is presented for purposes of clarity and is not meant as a description of prior art with respect to any claim.

(12) In some embodiment, a non-wetting, liquid-impregnated surface is provided that includes a solid having textures (e.g., posts) that are impregnated with an impregnating liquid. In general, solid features can be made from or comprise any material suitable for use in accordance with the present invention. In accordance with various embodiments of the present invention, micro-scale solid features are used (e.g., from 1 micron to about 100 microns in characteristic dimension). In certain embodiments, nano-scale solid features are used (e.g., less than 1 micron, e.g., 1 nm to 1 micron).

(13) In some embodiments, the liquid-impregnated surface is configured such that water droplets contacting the surface are not pinned or impaled on the surface.

(14) As used herein, emerged area fraction ϕ is defined as a representative fraction of the projected surface area of the liquid-impregnated surface corresponding to non-submerged solid at equilibrium. The term “equilibrium” as used herein refers to the condition in which the average thickness of the impregnating film does not change over time due to drainage by gravity when the substrate is held away from horizontal, and where evaporation is negligible (e.g., if the liquid impregnated liquid were to be placed in an environment saturated with the vapor of that impregnated liquid). Similarly, the term “pseudo-equilibrium” as used herein refers to the same condition except that evaporation may occur.

(15) In general, a “representative fraction” of a surface refers to a portion of the surface with a sufficient number of solid features thereupon such that the portion is reasonably representative of the whole surface. In certain embodiments, a “representative fraction” is at least a tenth of the whole surface.

(16) Referring to FIG. 1, a schematic cross-sectional view and the corresponding top view of a liquid-impregnated surface that is partially submerged is shown. The upper left drawing of FIG. 1 shows a cross-sectional view of a row of cone-shaped solid features. The projected surface area of the non-submerged solid 102 is illustrated as shaded areas of the overhead view, while the remaining non-shaded area represents the projected surface area of the submerged liquid-impregnated surface 100. In addition to the projection surface area of this row of solid features, other solid features placed in a semi-random pattern are shown in shade in the overhead view. Similarly, the cross-section view of a row of evenly spaced posts is shown on the right of FIG. 1. Additional rows of well-patterned posts are shown in shade in the overhead view. As demonstrated, in some embodiments of the present invention, a liquid-impregnated surface includes randomly and/or non-randomly patterned solid features.

(17) In certain embodiments of the present invention, ϕ is less than 0.30, 0.25, 0.20, 0.15, 0.10, 0.05, 0.01, or 0.005. In certain embodiments, ϕ is greater than 0.001, 0.005, 0.01, 0.05, 0.10, 0.15, or 0.20. In certain embodiments, ϕ is in a range of about 0 and about 0.25. In certain embodiments, ϕ is in a range of about 0 and about 0.01. In certain embodiments, ϕ is in a range of about 0.001 and about 0.25. In certain embodiments, ϕ is in a range of about 0.001 and about 0.10.

(18) In some embodiments, the liquid-impregnated surface is configured such that cloaking by the impregnating liquid can be either eliminated or induced, according to different embodiments described herein.

(19) As used herein, the spreading coefficient, S.sub.ow(a) is defined as γ.sub.wa−γ.sub.wo−γ.sub.oa, where γ is the interfacial tension between the two phases designated by subscripts w, a, and o, where w is water, a is air, and o is the impregnating liquid. Interfacial tension can be measured using a pendant drop method as described in Stauffer, C. E., “The measurement of surface tension by the pendant drop technique,” J. Phys. Chem. 1965, 69, 1933-1938, the text of which is incorporated by reference herein. Exemplary surfaces and its interfacial tension measurements (at approximately 25° C.) are shown in Appendix D, in particular, Table S2.

(20) Without wishing to be bound to any particular theory, impregnating liquids that have S.sub.ow(a) less than 0 will not cloak, resulting in no loss of impregnating liquids, whereas impregnating liquids that have S.sub.ow(a) greater than 0 will cloak matter (condensed water droplets, bacterial colonies, solid surface) and this may be exploited to prevent corrosion, fouling, etc. In certain embodiments, cloaking is used for preventing vapor-liquid transformation (e.g, water vapor, metallic vapor, etc.). In certain embodiments, cloaking is used for inhibiting liquid-solid formation (e.g., ice, metal, etc.). In certain embodiments, cloaking is used to make reservoirs for carrying the materials, such that independent cloaked materials can be controlled and directed by external means (like electric or magnetic fields).

(21) In certain embodiments, lubricant cloaking is desirable and is used a means for preventing environmental contamination, like a time capsule preserving the contents of the cloaked material. Cloaking can result in encasing of the material thereby cutting its access from the environment. This can be used for transporting materials (such as bioassays) across a length in a way that the material is not contaminated by the environment.

(22) In certain embodiments, the amount of cloaking can be controlled by various lubricant properties such as viscosity, surface tension. Additionally or alternatively, we can control the de-wetting of the cloaked material to release the material. Thus, it is contemplated that a system in which a liquid is dispensed in the lubricating medium at one end, and upon reaching the other end is exposed to environment that causes the lubricant to uncloak.

(23) In certain embodiments, an impregnating liquid is or comprises an ionic liquid. In some embodiments, an impregnating liquid can be selected to have a S.sub.ow(a) less than 0. Exemplary impregnating liquids include, but are not limited to, tetrachloroethylene (perchloroethylene), phenyl isothiocyanate (phenyl mustard oil), bromobenzene, iodobenzene, o-bromotoluene, alpha-chloronaphthalene, alpha-bromonaphthalene, acetylene tetrabromide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIm), tribromohydrin (1,2,3-tribromopropane), ethylene dibromide, carbon disulfide, bromoform, methylene iodide (diiodomethane), stanolax, Squibb's liquid petrolatum, p-bromotoluene, monobromobenzene, perchloroethylene, carbon disulfide, phenyl mustard oil, monoiodobenzene, alpha-monochloro-naphthalene, acetylene tetrabromide, aniline, butyl alcohol, isoamyl alcohol, n-heptyl alcohol, cresol, oleic acid, linoleic acid, amyl phthalate and any combination thereof.

(24) In accordance with the present invention, exemplary solid features include, but are not limited to, polymeric solid, a ceramic solid, a fluorinated solid, an intermetallic solid, and a composite solid and any combination thereof. As demonstrated in FIG. 1, solid features can comprise any suitable shapes and/or define any suitable structures. Exemplary solid features include, but are not limited to, pores, cavities, wells, interconnected pores, and interconnected cavities and any combination thereof.

(25) In some embodiments, solid features have a roughened surface. As used herein, θ.sub.os(a) is defined as the contact angle of oil (subscript ‘o’) on the textured solid (subscript ‘s’) in the presence of air (subscript ‘a’). In certain embodiments, the roughened surface of solid features provides stable impregnation of liquid therebetween or therewithin, when θ.sub.os(v)>θ.sub.c.

(26) In certain embodiments, liquid-impregnated surfaces described herein have advantageous droplet roll-off properties that minimize the accumulation of the contacting liquid on the surfaces. Without being bound to any particular theory, a roll-off angle α of the liquid-impregnated surface in certain embodiments is less than 50°, less than 40°, less than 30°, less than 25°, or less than 20°.

(27) Typically, flow through a pipe or channel, having a liquid-impregnated surface on its interior:

(28) $\begin{array}{cc}\frac{Q}{\Delta p\text{/}L}\sim \left(\frac{R^4}{{\mu }_1}\right)\left[1+\left(\frac{h}{R}\right)\left(\frac{{\mu }_1}{{\mu }_2}\right)\right]& \left(1\right)\end{array}$
where Q is the volumetric flow rate, R is pipe radius, h is the height of the texture, μ.sub.2 is the viscosity of lubricant and μ.sub.1 is the viscosity of the fluid flowing through the pipe. Δp/L is the pressure drop per L. Without being bound to any particular theory, it is believed that (h/R)(μ.sub.1/μ.sub.2) is greater than 1 for this to have a significant effect and this sets the height of the texture in relation to the viscosity ratio.

(29) Although modeled for pipe flow, the general principals also apply to open systems, where R is replaced with the characteristic depth of the flowing material. The average velocity of the flow ˜Q/A, where A is the cross-sectional area of the flowing fluid.

(30) For example, mayonnaise has a viscosity that approaches infinity at low shear rates (it is a Bingham plastic (a type of non-Newtonian material)), and therefore behaves like a solid as long as shear stress within it remains below a critical value. Whereas, for honey, which is Newtonian, the flow is much slower. For both systems, h and R are of the same order of magnitude, and μ.sub.2 is the same. However, since μ.sub.honey«μ.sub.mayonnaise, then

(31) $\begin{array}{cc}\left(\frac{h}{R}\right)\left(\frac{{\mu }_{\mathrm{honey}}}{{\mu }_2}\right)⪡\left(\frac{h}{R}\right)\left(\frac{{\mu }_{\mathrm{mayonnaise}}}{{\mu }_2}\right)& \left(2\right)\end{array}$
thus mayonnaise flows much more quickly out of the bottle than honey.

(32) According to some embodiments of the present invention, an article includes an interior surface, which is at least partially enclosed (e.g., the article is an oil pipeline, other pipeline, consumer product container, other container) and adapted for containing or transferring a fluid of viscosity μ.sub.1, wherein the interior surface comprises a liquid-impregnated surface, said liquid-impregnated surface comprising an impregnating liquid and a matrix of solid features spaced sufficiently close to stably contain the impregnating liquid therebetween or therewithin, wherein the impregnating liquid comprises water (having viscosity μ.sub.2). In certain embodiments, μ1/μ2 is greater than about 1, about 0.5, or about 0.1.

(33) In certain embodiments, the impregnating liquid comprises an additive to prevent or reduce evaporation of the impregnating liquid. The additive can be a surfactant. Exemplary surfactants include, but are not limited to, docosanoic acid, trans-13-docosenoic acid, cis-docosenoic acid, nonylphenoxy tri(ethyleneoxy) ethanol, methyl 12-hydroxyoetadecanate, 1-Tetracosanol, fluorochemical “L-1006”, and combination thereof. More details can be found in White, Ian. “Effect of Surfactants on the Evaporation of Water Close to 100 C.” Industrial & Engineering Chemistry Fundamentals 15.1 (1976): 53-59, the contents of which are incorporated herein by references. In addition or alternative, exemplary additives can be C.sub.16H.sub.33COOH, C.sub.17H.sub.33COOH, C.sub.18H.sub.33COOH, C.sub.19H.sub.33COOH, C.sub.14H.sub.29OH, C.sub.16H.sub.33OH, C.sub.18H.sub.37OH, C.sub.20H.sub.41OH, C.sub.22H.sub.45OH, C.sub.17H.sub.35COOCH.sub.3, C.sub.15H.sub.31COOC.sub.2H.sub.5, C.sub.16H.sub.33OC.sub.2H.sub.4OH, C.sub.18H.sub.37OC.sub.2H.sub.4OH, C.sub.20R.sub.41OC.sub.2H.sub.4OH, C.sub.22H.sub.45OC.sub.2H.sub.4OH, Sodium docosyl sulfate, poly(vinyl stearate), Poly (octadecyl acrylate), Poly(octadecyl methacrylate) and combination thereof. More details can be found in Barnes, Geoff T. “The potential for monolayers to reduce the evaporation of water from large water storages.” Agricultural Water Management 95.4 (2008): 339-353, the contents of which are incorporated herein by references.

EXPERIMENTAL EXAMPLES

Example 1

(34) FIG. 2 shows experimental measurements of water droplet mobility on liquid impregnating surfaces. FIG. 2a is a plot of roll-off angle α as a function of emerged area fraction ϕ, for different surfaces (feature spacing b varies). An ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIm) was used as a impregnating liquid in this work. The top inset (FIG. 2b) shows an SEM image of the BMIm impregnated texture and shows that the post tops are dry. In FIG. 2c, when the posts are further roughened by adding nanograss, they are covered with BMIm (bottom inset) and consequently, the roll-off angle decreases.

(35) The experiments of FIG. 2 demonstrate that liquid-impregnated surfaces can be engineered to provide resistance to impalement and to provide non-wettability, without requiring replenishment of impregnating fluid to make up for liquid lost to cloaking (BMIm is an example liquid that does not cloak in the presence of air and water), and without requiring replenishment of impregnating liquid to maintain coverage over the tops of the solid features.

(36) BMIm impregnated textures showed roll-off angles which increase as the spacing decreases. This observation shows that pinning is non-negligible in this case, and occurs on the emergent post tops (FIG. 2b). However, we were able to significantly reduce this pinning by adding a second smaller length scale texture (i.e., nanograss on the posts), so that BMIm impregnated the texture even on the post tops, thereby substantially reducing ϕ (though still non-zero) (see FIG. 2c). It is important to note that the reduction in the emergent area fraction ϕ is not due to the absolute size of the texture features; since the oil-water and oil-air interfaces typically intersect surface features at contact angles θ.sub.os(w) and θ.sub.ow(a), ϕ rather depends on these contact angles and feature geometry.

Example 2

(37) This Example demonstrates that condensation can be inhibited by preventing coalescence due to liquid cloaking.

(38) FIG. 3a shows an ESEM image sequence of condensation on a micropost surface impregnated with Krytox that has positive spreading coefficient on water (Sow>0). Condensation is inhibited as Krytox cloaks the condensed droplets. FIG. 3b illustrates cloaked condensate droplet depicting the thin film of condensate that spreads on the droplet. FIG. 3c shows an ESEM image sequence of condensation on micropost surface impregnated with BMIm that has negative spreading coefficient with water (Sow<0). FIG. 3b illustrates uncloaked condensate droplet depicting the three phase contact line of the water-vapor, water-lubricant, and lubricant-vapor interfaces on one end and pinning of the droplet at the dry post tops at the other end. FIG. 3e is a plot comparing variation of surface area fraction covered by condensed water droplets versus time on surfaces impregnated with Krytox (Sow>0, solid squares) and BMIm (Sow<0, open diamonds). FIG. 3f is a Plot comparing number of water droplets per unit area versus time on surfaces impregnated with Krytox (solid squares) and BMIm (open diamonds). The ESEM experiments were conducted under identical conditions (pressure=800 Pa, substrate temperature ˜3.6° C., beam voltage=25 kV and beam current=1.7 nA). In the analysis, t=0 s is defined as the first frame in which water drops can be identified.

(39) Referring to FIG. 4, the very high subcooling is sufficient for condensation rate to overcome the cloaking phenomenon for 10 cSt oil. The temperature of the peltier cooler was set at −5° C. The room temperature was 20° C., and the dew point in the conditions was 12° C. However, the barrier for coalescence is significantly higher on more viscous lubricant even at this high degree of subcooling. As a result, the droplets appear on 10 cSt oil as hemispherical shapes, whereas on more viscous lubricant their sphericity is significantly low.

Example 3

(40) This Example demonstrates that condensation can be inhibited by limiting nucleation on high viscosity liquids.

(41) Similar to the conditions described in Example 2, the temperature of the peltier cooler was set at −5° C. The room temperature was 20° C., and the dew point in the conditions was 12° C. As can be seen in FIG. 5, the condensation rate is significantly decreased as viscosity of the oil increases. This is because the more viscous an oil, the less rapid the deformation of its surface upon adsorption of vapor molecules. Whereas on low viscosity liquids, the more rapid change of curvature upon deformation leads a more rapid decrease in the energy barrier for condensation to proceed, and hence more rapid condensation.

Example 4

(42) This Example demonstrates that frost can be inhibited by limiting nucleation on high viscosity liquids.

(43) Similar to the conditions described above, the temperature of the peltier cooler was set at −15° C. The experiments were conducted in low relative humidity environment such the dew point in the conditions was −10° C. In these conditions, water vapor forms directly as frost on the peltier plate. However, on the impregnated surface, water vapor still forms as droplets, and frost. As can be seen in FIG. 6, the frost formation rate is significantly decreased as viscosity of the oil increases. On low viscosity liquid, the water phase show mobility signifying that water exists as supercooled droplets.

EQUIVALENTS

(44) While the invention has been particularly shown and described with reference to specific preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.