Articles and methods for levitating liquids on surfaces, and devices incorporating the same

Abstract

Methods described herein provide a way to reduce or eliminate drag and adhesion of a substance flowing over a surface by creating a vapor cushion via evaporation of a phase-changing material of or on the surface or encapsulated within textures of the surface. The vapor cushion causes the flowing substance to be suspended over the surface, greatly reducing friction, drag, and adhesion between the flowing substance and the surface. The temperature of the flowing substance is above the sublimation point and/or melting point of the phase-changing material. The phase-changing material undergoes a phase change (evaporation or sublimation) upon contact with the flowing substance due to local heat transfer from the flowing substance to the material, generating a vapor cushion between the solid or liquid material and the flowing substance.

Claims

1. A method of facilitating flow of a flowing substance on a surface comprising a phase-changing material, the method comprising: providing a surface comprising the phase-changing material having a melting temperature and/or sublimation temperature at operating pressure lower than the flowing substance temperature; and introducing the flowing substance onto the surface, thereby causing at least a portion of the phase-changing material to locally transition from a first state to a second state, thereby forming a lubricating intermediate layer between the flowing substance and the surface, wherein the phase-changing material is a liquid or a solid in the first state and a vapor in the second state.

2. The method of claim 1, wherein the surface is impregnated with the phase-changing material, the surface comprising a matrix of features spaced sufficiently close to stably contain the phase-changing material therebetween or therewithin.

3. The method of claim 1, wherein the flowing substance is a droplet.

4. The method of claim 3, further comprising the step of encapsulating biological matter into the droplet.

5. The method of claim 4, wherein the biological matter comprises DNA and/or RNA.

6. The method of claim 3, wherein the droplet has a volume in a range from between 0.1 pL to 1000 pL.

7. The method of claim 1, wherein the flowing substance is a solid at operating conditions.

8. The method of claim 1, wherein the flowing substance is a liquid at operating conditions.

9. The method of claim 1, wherein the flowing substance is a stream of liquid.

10. The method of claim 1, wherein the flowing substance is a stream of droplets.

11. The method of claim 1, wherein the surface is a coating on a substrate.

12. The method of claim 1, wherein a surrounding gas has a temperature that is lower than the melting temperature and/or sublimation temperature of the phase-changing material, so that the phase-changing material substantially remains in the first state in locations other than locations in contact with the flowing substance.

13. The method of claim 1, wherein the surface forms a channel over which or through which the flowing substance flows.

14. The method of claim 1, further comprising replenishing a supply of the phase-changing material.

15. The method of claim 1, wherein the phase-changing material is a liquid selected from kerosene, dichloromethane, acetone, ethanol, iodine, and naphthalene.

16. The method of claim 1, wherein the phase-changing material is dry ice.

17. The method of claim 1, wherein the phase-changing material is a solid selected from camphor and dry nitrogen.

18. The method of claim 1, wherein a volume of the flowing substance remains constant during transport.

19. The method of claim 1, wherein the phase-changing material in the first state and in the second state is unreactive and immiscible with the flowing substance.

20. The method of claim 1, wherein the surface is microtextured.

21. The method of claim 1, wherein the surface comprises the at least one phase-changing material positioned in a selected pattern, wherein the flowing substance flows over the surface according to the selected pattern.

22. The method of claim 21, wherein the pattern is a substantially V-shaped pattern, the method further comprising introducing a second flowing substance onto the surface, wherein the flowing substance and the second flowing substance flow along different branches of the substantially V-shaped pattern, the flowing substance and the second flowing substance merging at an apex of the substantially V-shaped pattern.

23. The method of claim 1, wherein the flowing substance is in contact only with the phase-changing material in the second state during transport.

24. The method of claim 1, wherein the flowing substance is a liquid having a melting and/or sublimation point that is higher than the melting and/or sublimation point of the phase-changing material.

25. A method of facilitating flow of a flowing substance on a surface comprising a phase-changing material, the method comprising: providing a surface comprising the phase-changing material having a melting temperature and/or sublimation temperature at operating pressure lower than the flowing substance temperature; and introducing the flowing substance onto the surface, thereby causing at least a portion of the phase-changing material to locally transition from a first state to a second state, thereby forming a lubricating intermediate layer between the flowing substance and the surface, wherein the phase-changing material is dry ice.

26. A method of facilitating flow of a flowing substance on a surface comprising a phase-changing material, the method comprising: providing a surface comprising the phase-changing material having a melting temperature and/or sublimation temperature at operating pressure lower than the flowing substance temperature; and introducing the flowing substance onto the surface, thereby causing at least a portion of the phase-changing material to locally transition from a first state to a second state, thereby forming a lubricating intermediate layer between the flowing substance and the surface, wherein a volume of the flowing substance remains constant during transport.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIGS. 1(a)-(d) illustrate is a schematic view of an Intermediate Layer (vapor) being generated between Material 1 and Material 2. The Material 2 has a temperature that is higher than the phase transformation point (melting point and/or the sublimation point) of Material 1. The contact between Material 2 and Material 1 causes a portion of the Material 1 that is in contact with Material 2 to transition to the Intermediate Layer state, which is a vapor state. FIGS. 1(a) and 1(b) correspond to states of complete levitation of Material 2. FIGS. 1(c) and 1(d) correspond to states of partial or intermittent levitation of Material 2. In FIGS. 1(b) and 1(d), the Material 2 has a temperature that is higher than the phase transformation point (melting point and/or the sublimation point) of Material 1 and the phase change temperature of Material 2 is higher than the phase change temperature of Material 1.

(3) FIG. 1(e) is a schematic view of a solid substrate 102 at least partially covered by a surface 104, the surface includes at least one phase-changing material, at least a portion of which transitions from its first original state to a second state upon contact with a droplet 108. Layer 106 is a lubricating intermediate layer between the droplet 108 and the surface 104.

(4) FIG. 1(f) is a schematic view of the droplet 108 of FIG. 1(e) after the droplet 108 has moved further in the shown flow direction. The intermediate layer 106 forms underneath the entire droplet 108.

(5) FIG. 1(g) is a schematic view of a stream of droplets 108 flowing over the surface 104. The conditions of operation may be selected such that the lubricating intermediate layer 106 is maintained between the stream of droplets 108 and the surface 104. In other words, the operating conditions may be selected such that there is a constant lubricating intermediate layer 106 between the stream of droplets 108 and the surface 104. The phase-changing material or materials within the surface 104 may be coupled to a replenishing source 120 that is configured to replenish an amount of the phase-changing material or materials within the surface 104 that is/are configured to transition to the second state. The surface 104 may include one or more sensors configured to transmit a signal to the replenishing source 120 to replenish an amount of the phase-changing material or materials within the surface 104 if an amount of the phase-changing material or materials within the surface 104 falls below a predetermined threshold. Each droplet 108 may be directed to a sorter/detector 122 that is configured to identify and sort the droplets 108. Although FIGS. 1(e) through 1(g) are shown and described with regards to droplets 108, those of ordinary skill in the art would appreciate that the droplet 108 could be any solid, liquid, or a stream of solids or liquids that is flowing over the surface 104.

(6) FIG. 2(a) is a schematic of liquid state on a typical hydrophobic surface in a state where the surface texture has not yet impaled the liquid.

(7) FIG. 2(b) is a schematic of liquid state on a typical hydrophobic surface in a state when the texture has impaled the liquid.

(8) FIG. 2(c) is a schematic of a flowing substance (suspended material (Material 2) being levitated or suspended through vaporization of an encapsulating substance (secondary material (Material 1)) within the surface textures of a solid substrate (solid) to eliminate contact between the flowing substance (suspended material (Material 2)) and the solid substrate (solid). Vaporization of the encapsulating substance (secondary material (Material 1)) results in formation of the intermediate lubricating vapor layer. In this embodiment, the flowing substance (suspended material) is shown in complete levitation mode. The flowing substance (suspended material) may remain in partial or intermittent levitation mode as well.

(9) FIG. 3 illustrates a sequence of water droplet impact on dry ice surface imaged at 3000 fps. The volume of the water droplet is roughly 5 μl. As can be seen, the droplet does not adhere to the dry surface, but instead bounces on it and eventually sheds the surface.

(10) FIG. 4 illustrates a sequence of water droplet impact on dry ice surface imaged at 3000 fps. The volume of the water droplet is roughly 5 μl. The water droplet was ejected at a large distance from the dry ice surface (height from which droplet ejected=20 cm)

(11) FIG. 5 illustrates a sequence showing motion of an ejected Alpha-Bromonaphthalene droplet on dry ice surface kept on paper imaged at 30 fps. As can be seen from the images, the droplet is very mobile on the surface. After t=0.12 seconds, the droplet leaves the dry ice surface and is absorbed by the paper and the region where the droplet is absorbed appears darker at t=0.20 seconds.

(12) FIG. 6 illustrates a sequence showing motion of an ejected high viscosity glycerol droplet on dry ice surface kept on paper imaged at 30 fps. As can be seen from the images, the droplet is very mobile on the surface. After t=0.16 seconds, the droplet leaves the dry ice surface and is trapped by the paper where it remains as a droplet.

(13) FIG. 7 illustrates a sequence of Tetraethyl orthosilicate jet ejecting on dry ice surface kept on paper imaged at 30 fps. As can be seen from the images, the surrounding paper is not wetted by the organic liquid. Instead it spreads and is absorbed within dry ice. Bubbles nucleate in the spreading liquid due to generation of carbon dioxide from the dry ice surface.

(14) FIG. 8 illustrates a sequence of a water droplet oscillating in an artificially created cavity patterned in dry ice. The pattern was created by forcing a steel disc kept at a higher temperature than dry ice, and pressed against dry ice. The lateral pressure due to the applied force results in very high sublimation of dry ice under the steel disc, thereby creating the cavity for water droplet to oscillate. Channels and cavities of various different shapes may be created.

(15) FIG. 9(a) illustrates a hemispherical pattern cut out in an underlying surface material.

(16) FIG. 9(b) illustrates a tube made of an underlying surface material.

(17) FIG. 9(c) illustrates an arbitrarily shaped channel patterned in an underlying surface material.

(18) FIG. 10 illustrates a system for facilitating flow of a flowing substance including a minichannel patterned on an underlying surface coated or covered with a phase-changing material. Droplets of two (or more) types of materials are introduced (e.g., via injection) into the system from two different channels. The droplets from the two different channels converge at an intersection point between the two channels, mix, and thereafter move along the transport channel.

(19) FIG. 11 illustrates artificial heating of a flowing substance material by means of a coaxially located laser supplying thermal energy to the flowing substance.

(20) FIG. 12 illustrates an example of an embodiment for making an encapsulated article using a phase-changing material. The embodiment illustrates two concentric tubes—an outer casing (solid surface) and an inner casing (slotted solid surface). The outer casing is a solid surface that provides strength to hold the entire article. The inner casing is a perforated tube through which the phase changing material is pushed towards the interior of the tube. The region between the outer and the inner casing is initially empty and is maintained at a constant separation distance that is denoted as the “feed through region.” The sublimating substrate material is generated or delivered from outside of the encapsulated article and then delivered to the article through the feed through region where, because of compression between the two concentric tubes, the phase-changing material flows towards an interior of the tube through the perforations of the inner casing, eventually forming a composite.

DESCRIPTION

(21) It is contemplated that apparatus, articles, 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 apparatus, articles, methods, and processes described herein may be performed by those of ordinary skill in the relevant art.

(22) Throughout the description, where apparatus and articles 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 apparatus and articles 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.

(23) 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.

(24) 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.

(25) In certain embodiments, micro-scale features are used (e.g., from 1 micron to about 100 microns in characteristic dimension). In certain embodiments, nano-scale features are used (e.g., less than 1 micron, e.g., 1 nm to 1 micron).

(26) Certain embodiments of the present invention relate to lowering the adhesion between two materials by creating an lubricating intermediate layer generated by a phase change (evaporation/sublimation) of at least one phase-changing material of or on the underlying surface as shown in FIGS. 1 and 1(e)-1(g). According to one embodiment, the intermediate layer includes a vapor layer formed by either evaporation of at least one phase-changing material (Material 1) from the underlying surface where the Material 1 is a liquid, or by sublimation of the at least one material (Material 1) from the underlying surface where the Material 1 is a solid. The underlying surface may include one or more phase-changing materials that exhibit different thermal properties.

(27) In one embodiment, the formation of the intermediate lubricating vapor layer may result in complete levitation of the flowing substance (suspended material), thus resulting in no contact between the flowing substance (suspended material) and the underlying surface (FIGS. 1(a) and 1(b)). In another embodiment, the formation of the intermediate lubricating vapor layer may result in partial levitation that results in decreased contact between the flowing substance (suspended material) and the underlying surface (FIGS. 1(c) and 1(d)). In yet another embodiment, the flowing substance (suspended material) may intermittently contact the underlying surface material (FIGS. 1(c) and 1(d)).

(28) Here, “complete levitation” is defined as the state where the flowing substance (suspended material) is separated by the intermediate lubricating vapor layer at all times during transport of the flowing substance (suspended material), “Partial levitation” is defined as the state where the flowing substance (suspended material) is in partial contact with the intermediate lubricating vapor layer at all times during transport of the flowing substance (suspended material). “Intermittent levitation” exists when the flowing substance (suspended material) exists in either “partial levitation” or “complete levitation” at different times during the transport of the flowing substance (suspended material).

(29) Whether the levitation is complete, partial, or intermittent may depend upon several factors including, but not limited to, a weight of the flowing substance (suspended material), the vaporization rate of the phase-changing material, the thermal properties of the flowing substance (suspended material), instabilities in the system and flow conditions of the flowing substance (suspended material). The flowing substance (e.g., a water droplet or film) can move on such intermediate lubricating vapor layer with negligible adhesion. In certain embodiments, partial or intermittent levitation of a wide variety of flowing substances is possible, which leads to very low adhesion of the flowing substance to the underlying surface.

(30) According to another embodiment of the present invention, the phase-changing material may be entrapped in a solid surface by means of impregnation as illustrated in FIG. 2(c). Liquid impregnated surfaces are described in U.S. patent application Ser. No. 13/302,356, entitled “Liquid-Impregnated Surfaces, Methods of Making, and Devices Incorporating the Same,” filed Nov. 22, 2011, the disclosure of which is hereby incorporated by reference herein in its entirety. Articles and methods that enhance or inhibit droplet shedding from surfaces are described in U.S. patent application Ser. No. 13/495,931, entitled, “Articles and Methods for Modifying Condensation on Surfaces,” filed Jun. 13, 2012, the disclosure of which is incorporated by reference herein in its entirety.

(31) According to certain aspects of the present invention, a solid substrate (e.g., pipeline) is covered at least in part by a solid or liquid surface. The solid or liquid surface may be poured, coated, laminated, or applied in any suitable way to the solid substrate. The solid or liquid surface includes or is composed of at least one phase-changing material that is configured to evaporate or sublimate upon contact with a flowing substance (solid or liquid) and to form a vapor layer between the flowing substance and the solid or liquid surface. In certain embodiments, a solid surface envelops the phase-changing material, such that the entire portion of the solid surface in contact with the flowing substance is covered with the phase-changing material.

(32) A large class of solid and liquid phase-changing materials exist that can vaporize at different temperatures; thus, the low adhesion through vapor cushion can be obtained at temperatures that are significantly below the Leidenfrost temperature of water. Thus, aspects of the present invention do not require expanding significant energy to heat the underlying solid or liquid surface to the Leidenfrost temperature of water to suspend water droplets over a surface. A flowing substance may be suspended even at room temperatures by using a surface that includes a phase-changing material having a high vapor pressure at room temperatures. Moreover, the suspension of a flowing substance may be achieved at low temperatures (e.g., below or significantly below room temperature) by selecting an appropriate solid or liquid phase-changing material of or on the surface or encapsulated within textures of the surface that can vaporize at such low temperatures.

(33) Furthermore, in contrast with the Leidenfrost phenomenon, which results in the loss (via evaporation) of the flowing substance (water), aspects of the present invention relate to articles and methods that result in no loss or only negligible loss of the flowing substance. Only the phase-changing material that evaporates or sublimates is dissipated when the flowing substance flows over the surface. The volume and amount of the flowing substance remains constant during transport. Furthermore, the flowing substance remains intact during transport; moreover, aspects of the present invention relate to reducing and preventing contamination of the flowing substance by cutting off or preventing oxygen, dust particles, and other contaminants from reaching the flowing substance. Certain embodiments relate to creating the intermediate lubricating vapor layer that may envelop the flowing substance, thus preventing contaminants and other particles from reaching the flowing substance.

(34) Contact Regimes of Suspended Flowing Substance and the Substrate Material

(35) The contact area between the flowing substance (solid or liquid) and the underlying surface including the phase-changing material(s) is determined by the thickness and uniformity of the intermediate layer that is generated by the phase-changing material(s) on or of the underlying surface. The intermediate layer thickness is determined by the evaporation/sublimation rate of the phase-changing material(s). As discussed above, three states of levitation are possible—complete, partial, and intermittent levitation.

(36) Complete levitation is the state where the flowing substance is separated by the intermediate layer at all the times, thus resulting in no contact between the flowing substance and the underlying surface (e.g., FIGS. 1(a) and 1(b)). For a flowing substance of density ρ.sub.d, and radius R.sub.d, the body forces are given by ρ.sub.dR.sub.d.sup.3g. For complete levitation, the evaporation rate needs to be sufficient to counter this body force. If the phase-changing material is evaporating/sublimating at a rate of {dot over (m)}.sub.v kg/s, and generates a vapor velocity of U.sub.v m/s, then for complete levitation:

(37) $\begin{array}{cc}{\rho }_d{R}_d^{3}g\text{~}{\stackrel{.}{m}}_v{U}_v\text{~}{\rho }_v{R}_d^2{U}_v.fwdarw.U_v\text{~}\frac{{\rho }_{d}g}{{\rho }_v}{R}_d& \left(1\right)\end{array}$

(38) Thus, if the phase-changing material generates vapor with flow given by Equation (1), a flowing substance may be completely suspended on the generated vapor cushion.

(39) Partial levitation is the state where the flowing substance is in partial contact with the intermediate lubricating vapor layer at all times, resulting in decreased contact between the flowing substance and the underlying surface (e.g., FIGS. 1(c) and 1(d)).

(40) Intermittent levitation is a state where the flowing substance is in either partial levitation or complete levitation at different times during the transport of the flowing substance, and thus the flowing substance may intermittently contact the underlying surface (e.g., FIGS. 1(c) and 1(d)). Certain embodiments relate to selecting an appropriate phase-changing material and/or operating conditions to achieve a desired levitation regime of the flowing substance.

(41) Even in absence of complete levitation, the presence of an intermediate lubricating vapor layer decreases the adhesion between the flowing substance and the underlying surface even by making the contact intermittent in nature. Depending upon the mode in which the intermediate layer is formed, localized formation of vapor cushion is possible causing reduction in adhesion forces between the flowing substance and the underlying material. Vapor mechanisms of intermediate layer formation are discussed below.

(42) Generation of Intermediate (Vapor) Layer

(43) The phase-changing material may be a sublimating solid, an evaporating liquid, a composite of a non-sublimating and a sublimating solid, or a composite of evaporating liquid and a non-sublimating solid. Regardless of the phase-changing material composition in the above-mentioned ways, the vapor intermediate layer may be produced by either of the following six mechanisms described below: (1) natural evaporation from a liquid; (2) natural sublimation from a solid; (3) forced evaporation from a liquid by external heating; (4) forced sublimation from a solid by external pressure change; (5) evaporation by contact heat transfer; and (6) sublimation by contact heat transfer.

(44) Natural Evaporation from a Liquid

(45) Evaporation occurs when a liquid substrate (designated by A) at a temperature T.sub.liquid is surrounded by a gas mixture (designated by B) with unsaturated vapor component at temperature T.sub.surrounding. If the diffusion coefficient of the vapor of the substrate liquid in the surrounding gas mixture is D.sub.AB m.sup.2/s, then the rate of mass transfer to the surrounding is given by
{dot over (m)}.sub.c∝D.sub.AB(ρ.sub.A*−ρ.sub.A∞)  (2)
where ρ.sub.A∞ is the density of vapor at large distances from the liquid substrate, and ρ.sub.A* is the density of vapor just near the liquid substrate and given by the saturation condition. Examples of such phase-changing liquid materials include acetone, ethanol, various organic liquids, and any combination thereof.
Natural Sublimation from a Solid

(46) Sublimation occurs when a solid substrate changes directly from its solid state to a vapor state at temperatures and pressures below the solid substrate's triple point in the phase diagram. Thus, a solid substrate exposed to a system with pressure P and temperature T, and having a sublimation temperature T.sub.sublimation will continuously be converted into vapor. Similar to evaporation from a liquid described above, the rate of mass transfer is given by {dot over (m)}.sub.c∝D.sub.AB(ρ.sub.A*−ρ.sub.A∞) where ρ.sub.A∞ is the density of vapor at large distances from the solid substrate, and ρ.sub.A* is the density of vapor just near the solid substrate and given by the saturation condition. Examples of such phase-changing solid materials include dry ice (solid carbon dioxide).

(47) Forced Evaporation from a Liquid by External Heating

(48) From Equation 2 above, it can be seen that the rate of evaporation can be increased by increasing the vapor density difference (ρ.sub.A*−ρ.sub.A∞). This is achieved by increasing the saturated conditions of the vapor by increasing the temperature of the liquid T.sub.liquid and hence the ρ.sub.A* . The upper limit of the heating temperature being the boiling temperature of the substrate liquid at the given operating pressure. Thus, by heating the volatile liquid to a higher temperature, the evaporation rate and hence the thickness of the intermediate layer may be increased. Examples of such liquid phase-changing materials include acetone, ethanol, various organic liquids, and any combination thereof.

(49) Forced Sublimation from a Solid by External Pressure Change

(50) From Equation 2 above, it can be seen that the rate of sublimation can be increased by increasing the vapor density difference (ρ.sub.A*−ρ.sub.A∞). This is achieved by decreasing the pressure of the system or increasing a temperature of the phase-changing material. Examples of such materials include Iodine, Naphthalene that directly sublimate upon heating.

(51) Evaporation by Contact Heat Transfer

(52) If a liquid phase-changing material at a temperature T.sub.liquid surrounded by a gas mixture at temperature T.sub.surrounding is brought into contact with a flowing substance (solid or liquid) such that the flowing substance temperature T.sub.material is higher than the boiling point of the liquid phase-changing material T.sub.BP, then the contact of the two materials may result in a localized phase change of the liquid phase-changing material, thereby creating the vapor layer.

(53) Sublimation by Contact Heat Transfer

(54) If a solid substrate including or coated with a solid phase-changing material at a temperature T.sub.solid surrounded by a gas mixture at temperature T.sub.surrounding is brought into contact with a flowing substance (solid or liquid), such that the flowing substance temperature T.sub.material is higher than the sublimation temperature of the solid phase-changing material, T.sub.sublimation, then the contact of the two materials may result in a localized phase change of the solid phase-changing material, thereby creating the vapor layer. In embodiments when the flowing substance is a liquid, the flowing substance can be prevented from spreading on the sublimating solid phase-changing material if the freezing point of the flowing liquid is higher than the sublimation temperature of the phase-changing material.

(55) Decreased Adhesion Due to Phase Change of the Underlying Surface

(56) As discussed above, the suspended flowing substance may either be a liquid or a solid object. The underlying solid or liquid surface may either be or may include a phase-changing solid, liquid or a composite of solid and liquid phase-changing materials.

(57) FIG. 3 shows a sequence of impacts of a water droplet that has been ejected on the surface of dry ice from a height comparable to the size (diameter) of the droplet. The ejected water droplets are at room temperature, whereas the underlying dry ice surface is sublimating at a constant temperature of about −78° C. as the experiments are carried at room pressure conditions. The sequence shows that water droplets instead of getting frozen instantly interact with the underlying phase-changing dry ice material and result in heat transfer from the water droplet to the underlying phase-changing dry ice material resulting in localized enhanced sublimation of the dry ice. As a result, the dry ice underneath the water droplet gets converted into a vapor layer, which results in a marked decrease in adhesion of water droplets with the dry ice in its original solid state. Since the freezing point of water (0° C.) is higher than the sublimating temperature of dry ice, the water instead of spreading on dry ice remains in a droplet shape. In other words, the sublimation of the dry ice results in the water droplets contacting primarily or only the vapor layer generated by sublimation of the dry ice as opposed to contacting the dry ice in the solid state. As can be seen from the image sequence in FIG. 3, the underlying dry ice surface has a very slight tilt angle (<2°) and the water droplet shows very low adhesion to the underlying dry ice surface, and sheds from the underlying dry ice surface eventually.

(58) FIG. 4 shows water droplet impact behavior on a dry ice surface when the droplet was ejected at large distance (e.g., significantly larger than the diameter of the droplet) away from the dry ice surface (water droplet ejection height=20 cm). The water droplet impacts, spreads, and disintegrates into many smaller droplets that continue to roll on the dry ice surface as shown in FIG. 4. Again, since the freezing point of water (0° C.) is higher than the sublimation temperature of dry ice, the water instead of spreading on dry ice, remains in droplet shape. The conditions under which the flowing substance is introduced over the solid or liquid surface including a phase-changing material differ depending on the desired effect. For certain flowing substances, whether or not the flowing substance impacts, spreads and disintegrates into smaller droplets or particles is insignificant, while it is significant for other applications. Thus, a manner in which the flowing substance is introduced to the surface may be adjusted depending on a desired manner of flow of the flowing substance.

(59) Omniphobicity of a Variety of Liquids

(60) For the working of our idea, it is critical that the intermediate lubricating vapor layer be established either by natural causes (natural evaporation from a liquid or natural sublimation from a solid) or forced causes (forced evaporation from a liquid by external heating or forced sublimation from a solid by external pressure change) or by contact heat transfer (evaporation by contact heat transfer or sublimation by contact heat transfer).

(61) FIGS. 5 and 6 show cases where two materials—alphabromonaphthalene and glycerol are ejected on a dry ice surface and their interaction results in contact heat transfer from these suspending materials to dry ice. Each material has a melting point that is higher than the temperature of the dry ice (same as sublimation temperature of dry ice of −78° C.). As a result, both of these materials roll on the dry ice surface instead of spreading.

(62) On the other hand, FIG. 7 shows the case where the material—tetraethyl orthosilicate droplet—spreads on dry ice. This liquid has a freezing point (−78° C.) that is comparable to dry ice sublimation temperature. As a result, this liquid cannot transfer sufficient heat to vaporize the dry ice, and it directly spreads on the dry ice. The bubbles that are observed at times after t=0.12 s are formed because of carbon dioxide gas generated by vaporization of dry ice in contact with the flowing substance. A list of various materials that may spread or roll is shown in Table 1 below.

(63) TABLE-US-00001 TABLE 1 List of Materials that Spread or Roll Away on Dry Ice Surface Tension, Dynamic Kinematic MP hfg hfg + Liq Viscosity, Liq Viscosity, Liq CAS ° C. kJ/kg CliqΔT1 mN/m or dyn/cm cP cSt Spreads? Tetraethyl orthosilicate 78-10-4 −78 Y trichlorovinylsilane 75-94-5 −95 Y Hexane 110-54-3 −95.16 171.057 390.1074522 17.98091517 0.286218927 0.43613885 Y Heptane 142-82-5 −90.43 140.014 365.3677443 19.77681872 0.402551947 0.590530499 Y Ethyl Acetate 141-78-6 −83.7 118.947 308.7606708 23.24044626 0.420240359 0.470390523 Y pentane 109-66-0 −129.73 116.438 338.6958283 15.46605533 0.245270362 0.394807534 Y Ethanol 64-17-5 −114.4 108 336.4596796 23.38597471 1.041758346 1.323400893 Y Acetone 67-64-1 −95 97.99 313.1729369 23.04083028 0.31114062 0.396011821 Y Toluene 108-88-3 −95 71.847 239.3461512 27.92544186 0.565450807 0.653932496 Y CO2 124-38-9 −78 Water 0 334 417.66 72 0.89 N Ethanolamine 141-43-5 10.65 335.538 368.0345905 50.24550288 22.16725894 21.86773596 N propylene glycol 57-55-6 −60 99.48 322.6950712 35.47006509 48.99417181 47.4532577 N Decane 124-18-5 −29.51 201.849 311.0172571 23.40590276 0.835779944 1.147257355 N Dodecane 112-40-3 −9.43 216.04 281.1068158 24.9390154 1.357389348 1.822018018 N Tetradecane 629-59-4 5 227.176 260.3015124 26.15179745 2.052424839 2.708083711 N Ethylene Glycol 107-21-1 −12.4 160.436 246.8327712 49.89191875 17.19415434 15.49171193 N Hexadecane 544-76-3 17 235.641 242.2904979 27.0868661 3.127040173 4.060217401 N Diethylene glycol 111-46-6 −10.3 154.54 228.3087359 49.53865475 29.10512223 26.12913981 N formamida 75-12-7 2.55 177.171 218.8663302 59.41123634 3.397153179 3.008767657 N Glycerol 56-81-5 18.33 198.535 202.5046541 65.15998508 747.1141884 594.4756088 N dimethyl sulfoxide 67-68-5 18.7 183.912 186.3790333 43.78274035 2.005994401 1.830903246 N 1234tetrahydronaphthale 119-64-2 −35.75 94.172 185.8649022 33.15802758 2.046945373 2.116575107 Beads oleic acid 112-80-1 13.53 140.193 155.8680584 32.34042661 29.28821752 32.98492136 N bromobenzene 108-86-1 −30.72 67.684 117.8223173 35.91432672 1.003555172 0.674659794 Beads 1-Bromnaphthalene 90-11-9 6.35 73.405 88.68826053 44.38748057 3.713082848 2.511937393 N 1,2,3-tribromopropane 96-11-7 16.19 82.17 85.0959112 46.52288885 3.737720492 1.550352255 N Cyclohexane 110-82-7 6.47 31.844 57.89907132 24.6518243 0.918205149 1.187571686 N Silicone Oil 1000 cSt 63148- −59 N 62-9
Directed Flow and Patterning of Substrate

(64) In a particular embodiment where the surface includes a sublimating solid (e.g., dry ice) the surface can be patterned to allow the control of movement of a flowing substance thereon. FIG. 8 illustrates a sequence of images of a water droplet oscillating in an artificial minichannel created in dry ice. Patterning of desired shapes may be performed by a variety of methods in order to cause preferential enhanced sublimation. According to one embodiment shown in FIG. 8, the illustrated pattern was created by forcing a steel disc kept at a higher temperature than dry ice pressed against the dry ice surface. The lateral pressure due to the applied force results in a large amount of sublimation of dry ice under the steel disc. In certain embodiments, the methods to create patterns in or on the underlying surface including or covered with the phase-changing material (e.g., dry ice) include, but are not limited to, pressing, cutting, slicing etc. Various patterned surfaces are shown in FIGS. 9(a)-(c).

(65) In certain embodiments, where dry ice is the underlying surface or is included on the underlying surface, channels of any desired shapes may be patterned directly on the dry ice material. Contamination is avoided since dry ice produces carbon dioxide that may envelop the flowing substance.

(66) According to another embodiment of the present invention, the surface over which the flowing substance flows may include channels that are substantially V-shaped, substantially U-shaped, or are shaped in any desired manner. Such channels may be useful, for example, to facilitate a chemical reaction. If the channel is substantially V-shaped as the channel shown in FIG. 10, a first flowing substance may be introduced at a corner of a first branch of the substantially V-shaped channel (e.g., location of droplet 1 introduction), and a second flowing substance may be introduced at a corner of a second branch of the substantially V-shaped channel (e.g., location of droplet 2 introduction). The first and second flowing substances may then be directed to flow towards and merge at an apex of the substantially V-shaped channel and then flow along the transport channel as shown in FIG. 10. Certain embodiments relate to merging and reaction of microscopic/nanoscopic quantities of reactants together—since there is no stiction of the flowing substance on the underlying surface.

(67) Achieving Temperature Stabilization of Flowing (Suspended) Substances

(68) The decrease in contact due to formation of an intermediate layer by vaporization of a phase-changing material is based on heat and mass transfer from the phase-changing material in conjunction with its interaction with the flowing substance. This requires a temperature difference between the flowing substance and the phase-changing material when the vaporization rate from the phase-changing material alone is not sufficient to levitate the flowing substance

(69) $\left(e.g.,\mathrm{when}{U}_v<\frac{{\rho }_{d}g}{{\rho }_v}{R}_d\right).$
This is particularly important for transporting flowing substances over long distances. The phase-changing material and the flowing substance continuously exchange heat via either direct contact (in case of intermittent or partial levitation) and through the intermediate lubricating vapor layer (in all cases). This results in a decrease in the temperature of the flowing substance to the point where the temperature of the flowing substance and the phase-changing material achieve equilibrium with each other, preventing or disruption the generation of the intermediate lubricating layer, which leads to high adhesion between the flowing substance and the underlying surface including the phase-changing material. Further, when the flowing substance is a liquid or a liquid encapsulating other components, and the phase-changing material is a sublimating solid (e.g., dry ice), reaching the above-referenced equilibrium state will result in freezing of the liquid.

(70) The equilibrium state may be prevented by artificially heating the flowing substance. An example of a system including an artificial heating component (e.g., laser) is shown in FIG. 11.

(71) Referring to FIG. 11, a laser with sufficient power to heat the flowing substance is centered on the transport path of the channel and a droplet is injected in the patterned minichannel. As the droplet interacts with the phase-changing substrate material in either complete, partial, or intermittent levitation mode, the droplet temperature decreases due to heat exchange between the substrate phase-changing material and the flowing substance. However, since the laser pulses are directed towards the flowing substance, the energy from the laser is absorbed by the flowing substance which results in an increase of temperature of the droplet. In an equilibrium state, the laser provides enough energy to the flowing substance to maintain the temperature of the flowing substance at a value that is higher than the temperature of the substrate phase-changing material. The choice of laser power required for maintaining the temperature of flowing substance at an elevated level depends upon multiple factors that include, but are not limited to, the volume of the flowing substance, the transport path length of the minichannel, the temperature of the substrate material, and other factors. Examples of laser types that may be required to achieve this state includes infra-red lasers, Nd:YAG lasers, helium lasers, and other suitable lasers. The minimum power requirement of the laser is about 5 mW, while the upper limit is set by a laser power that can heat the flowing substance without boiling it and/or without disrupting the integrity of the flowing substance. Other mechanisms through which heat can be supplied to the flowing substance include infra-red light and other suitable mechanisms.

(72) Substrate Usage Techniques

(73) In various embodiments, the methods and systems described herein may be used in at least the following two ways: (1) replaceable phase-changing substrates and (2) phase-changing substrates that may be replenished.

(74) Replaceable Substrates

(75) According to one embodiment, the patterned substrate phase-changing material may be used until it is entirely depleted (e.g., by vaporization loss) and may then be replaced by a similarly patterned substrate phase-changing material. This type of system has several advantages. One of the advantages is that vaporization of the phase-changing substrate material enables the creation of a self-cleaning system that requires negligible maintenance. In embodiments where the flowing substances are hazardous in nature (e.g., acids, bases, pathogen encapsulating liquids, etc.), a constantly vaporizing material envelops these hazardous materials and thereby blocks the supply to outside pollutants including oxygen, dust, etc. Moreover, removal of the phase-changing substrate material minimizes the need for environmental cleaning of the phase-changing substrate after transport. Conventional systems, such as systems using regular surfaces not coated with materials promoting flow of the flowing substances, require multiple cleaning operations before and/or after transport of the flowing substances. Such cleaning operations include acetone wash, DI water wash, etc, These operations create organic waste, the disposal and management of which requires a significant amount of monetary and time expenditures.

(76) Substrate Material is Replenished

(77) In certain embodiments, particularly where the phase-changing substrate material is a liquid, the replenishment of the phase-changing material can be accomplished by means of providing micro/nano textures on the solid substrate holding the phase-changing liquid. Particularly in embodiments where liquid impregnated surfaces are employed, this replenishment can be achieved by tuning the texture properties, and by other means such as providing an artificial reservoir of the volatile liquid close to the textured substrate such that a part of the textured substrate is in contact with such a reservoir, so that the volatile liquid can wick into the textured substrate by capillary action.

(78) In embodiments where the phase changing material is a sublimating substrate (e.g., dry ice), dry ice can be generated in-situ. The solid substrate may include perforations (holes, slits, etc.) at its bottom to sustain pressures required for generation of sublimating solids that are squeezed through such perforations and eventually rise to reach an equilibrium level within the solid. An example of such an embodiment is shown in FIG. 12.

(79) Specifics of Phase-Changing Material

(80) Some common desirable requirements for the surfaces useful according to embodiments of the present invention include both the phase-changing material as well as its vapor being unreactive and immiscible with the flowing substance and with the solid substrate over which the surface including the phase-changing material(s) may be positioned or which holds the phase-changing material. Further, the choice of the phase-changing material(s) for such applications will depend upon the thermodynamic conditions. Suitable liquids for the phase-changing material can be obtained that have large vapor pressure (high volatility). These liquids can further be heated so as to increase vapor flux, and the supplied heat is such that these liquids never attain their flash point to avoid combustion or related unwanted phenomena to occur.

(81) Some common liquids that can be used as the phase-changing material when the flowing substance is water are: kerosene, dichloromethane, etc. Some common solids that can be used as the phase-changing material when the flowing substance is water include dry ice, camphor, dry nitrogen.

(82) Examples of Flowing Substances (Suspended Materials)

(83) The flowing substance is non-reactive towards and immiscible with the substrate phase-changing material (in solid, liquid, or vapor phase). Examples of suitable flowing substances include organic liquids (examples of such liquids is provided in Table 1 above), water, any compatible solids, nanofluids, biofluids (e.g., plasma, blood, etc.), liquids containing or encapsulating other components (e.g., pathogens, antibodies, viruses, cell cultures, nucleic acids, etc.), compatible acids, and compatible bases (including those provided in Table 1 above). The methods described herein are capable of reducing adhesion of a large variety of liquids, including low surface tension liquids, high viscosity liquids, etc.

(84) Additional Applications

(85) As discussed above, the present invention may be used in a variety of applications and industries where contact between materials is of concern.

(86) According to one embodiment, the present invention may be used in pharmaceutical and drug related industries to carry out in-situ chemical reactions. As described above, a channel of a desired shape (e.g., substantially U-shape or V-shape) may be carved out in the solid or liquid surface including the phase-changing material (e.g., dry ice). Two flowing substances may then be introduced into opposing points (e.g., opposing corners of the substantially V-shaped channel), and the two flowing substances may be configured to travel towards a central or merging point (e.g., apex of the substantially V-shaped channel) to merge, mix, and to then be transported to a desired location. The dry ice (or the phase-changing material that is used) may be replenished by a replenishing chamber as needed at any point during the reaction. According to certain other embodiments, an underlying surface that is coated, covered, or patterned with a phase-changing material may be used only until the phase-changing material is entirely depleted, and the underlying surface may then be replaced with a new similarly coated, covered, or patterned underlying surface.

(87) Vaporization of the phase-changing materials enables the creation of self-cleaning systems which require negligible maintenance. In contrast, conventional methods require regular cleaning of the underlying surfaces, tubes, assemblies, etc.

(88) According to a further aspect of the present invention, the present invention may be used in microfluidic and/or bio-related applications. For example, nano- or picoliter-sized droplets can encapsulate biology (e.g., DNA or RNA) where single-plex polymerase chain reactions (PCRs) are performed in each droplet, and the droplets are transported for sorting, detection, etc. The volume of each droplet may range between, e.g., 0.1-1000 pL; 1-10 pL; 1-100 pL, or any other suitable size for bio-related applications.

(89) The present invention may also be used in continuous-flow microfluidics, digital microfluidics, DNA chips, molecular biology applications, study of evolutionary biology study of microbial behavior, cellular biophysics, optofluidics, fuel cell applications, acoustic droplet ejection, and all other suitable microfluidic applications. Aspects of the present invention may be used for enzymatic analysis, DNA analysis, molecular biology applications (e.g., various electrophoresis and liquid chromatography applications for proteins and DNA, cell separation, including separation of blood cells, cell manipulation and analysis, including cell viability analysis).

(90) Aspects of the present invention also relate to oil and gas applications, and in particular to liquid transportation through pipes, which requires huge pumping power, especially when done over long distances. By suitably choosing the vaporizing/sublimating material (which may encapsulate the solid substrate such as a pipe), large slip can be induced by eliminating the contact line pinning at solid interface, thereby drastically reducing drag and pumping power. According to certain embodiments, water could line the walls of pipelines. Oil that is forced into pipelines is heated, and this heat causes the water lining or a part of the water lining to evaporate, thus creating a vapor layer underneath. This greatly reduces the drag on the flowing oil and reduces the required pumping power.

(91) Aspects of the present invention may also be used for transporting chemicals/liquids in sealed environments without contact with solid surface.

(92) Aspects of the present invention may also be used for aircraft and utilities applications. Since surfaces encapsulated or coated with a vaporizing/sublimating material result in diminished ice/frost adhesion, the energy and environmentally harmful chemicals required to device aircraft wings can be significantly reduced. Similarly, ice from power transmission lines can be easily removed. Icing can be significantly reduced on wind turbines as well, therefore increasing their efficiency.

(93) Embodiments of the present invention may also be used for steam and gas turbines. Water droplets entrained in steam impinge on turbine blades and stick to them, thereby reducing turbine power output. By encapsulating a phase-changing material in a surface or by coating or applying such a phase-changing material onto the surface, droplets can be shed off the blades, and turbine power output can be significantly improved.

(94) Similar to ice adhesion challenges, surfaces encapsulated or coated with phase-changing materials can also be used to reduce adhesion of natural gas hydrates in oil and gas pipelines to reduce hydrate plug formation in deep sea applications. These surfaces can also be applied for reducing scaling (salt formation and adhesion).

EQUIVALENTS

(95) 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.