MATTER-REPELLENT SLIPPERY COATINGS AND MANUFACTURE THEREOF
20230220173 · 2023-07-13
Inventors
Cpc classification
C08L2205/22
CHEMISTRY; METALLURGY
C08L27/18
CHEMISTRY; METALLURGY
C09K3/18
CHEMISTRY; METALLURGY
C08J7/0427
CHEMISTRY; METALLURGY
International classification
C08L27/18
CHEMISTRY; METALLURGY
Abstract
A matter-repellent colloid-infused smooth surface (CISS) device has a solid substrate with a smooth surface where a thin coating of a non-volatile lubricating fluid and a plurality of nanoparticles and/or microparticles reside on the surface. The non-volatile lubricating fluid can be a perfluorinated fluid and the nanoparticles and/or microparticles can be polytetrafluoroethylene (PTFE) to provide a slippery surface to a metal, ceramic, glass, or plastic substrate. As needed, the smooth surface of the substrate can be modified with a silylating agent that is miscible with the lubricating fluid to enhance the stability of the coating smooth surface interface. In this manner, tubes, catheters, vials, bottles, or other devices can be imparted with a slippery surface that repels most gases, liquids, and solids.
Claims
1. A colloid-infused smooth surface (CISS) device comprising: a solid substrate with a smooth surface; and a coating comprising: a non-volatile lubricating fluid; and a plurality of nanoparticles and/or microparticles.
2. The CISS device according to claim 1, wherein the non-volatile lubricating fluid comprises a perfluorinated fluid.
3. The CISS device according to claim 2, wherein the perfluorinated fluid is selected from FC-70 and Chemours™ Krytox™ oils.
4. The CISS device according to claim 1, wherein the nanoparticles and/or microparticles comprise polytetrafluoroethylene (PTFE).
5. The CISS device according to claim 1, wherein the nanoparticles and/or microparticles are 0.01 to 0.06 mass fraction of the coating.
6. The CISS device according to claim 1, wherein the solid substrate comprises a metal, ceramic, glass, or plastic.
7. The CISS device according to claim 1, wherein the smooth surface has a roughness factors from 1.00 to 1.45.
8. The CISS device according to claim 1, wherein the smooth surface is silylated with a silylating agent missible with the non-volatile lubricating fluid.
9. The CISS device according to claim 8, wherein the lubricating fluid is selected from FC-70 and Chemours™ Krytox™ oils and the silylating agent is 1H,1H,2H,2H-perfluorodecyltrichlorosilane.
10. The CISS device according to claim 8, wherein the non-volatile lubricating fluid is a silicone oil and the nanoparticles and/or microparticles comprise silica particle.
11. The CISS device according to claim 8, wherein the non-volatile lubricating fluid is a hydrocarbon oil and the nanoparticles and/or microparticles comprise waxes, polyethylene, or alkyl functionalized silica particle.
12. A method of forming a solid device comprising a CISS that repels gases, liquids, and solids, comprising: providing a solid object with a smooth surface; and coating the smooth surface with a colloidal suspension comprising: a non-volatile lubricating fluid; and a plurality of nanoparticles and/or microparticles.
13. The method according to claim 12, wherein the solid object comprises a metal, ceramic, glass, or plastic.
14. The method according to claim 12, wherein coating comprises dip coating, roll coating, or spraying.
15. The method according to claim 12, wherein the non-volatile lubricating fluid comprises a perfluorinated fluid.
16. The method according to claim 15, wherein the perfluorinated fluid is selected from FC-70 and Chemours™ Krytox™ oils.
17. The method according to claim 12, wherein the nanoparticles and/or microparticles comprise PTFE.
18. The method according to claim 12, wherein the nanoparticles and/or microparticles are 0.01 to 0.06 mass fraction of the colloidal suspension.
19. The method according to claim 12, wherein the solid device is a tube, a vial, or a bottle.
20. The method according to claim 12, further comprising silylatating the solid object with a smooth surface with a silylating agent missible with the lubricating fluid.
21. The method according to claim 20, wherein the perfluorinated fluid is selected from FC-70 and Chemours™ Krytox™ oils and the silylating agent is 1H,1H,2H,2H-perfluorodecyltrichlorosilane.
22. The method according to claim 12, wherein the CISS repels hydrocarbons, mineral oil, water, ethanol, silicone oils, glycerol, ethylene glycol, dimethylformamide, honey, ketchup, toothpaste, and peanut butter.
23. A self-healing omniphobic device, comprising a CISS according to claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DISCLOSURE OF THE INVENTION
[0041] In embodiments colloid-infused smooth surfaces (CISSs), as illustrated in
[0042] A colloid lubricating film on a smooth solid is essentially attributed to the introduction of nano/microparticles that is able to produce a mobile structural roughness to stabilize the lubricant oil. For analysis of the interfacial interaction between a colloid and a test liquid, the effect of the nano/microparticles, the particles are treated as forming a structured surface with a roughness factor r.sub.p. The particles must have a preferential affinity for the lubricant liquid rather than the test liquid, such that the test liquid freely floats on the lubricant oil stabilized on the particle-induced roughed surface. The total interfacial energy of three wetting configurations on the particle surfaces can be considered. The first case is that the particle surface is completely wetted by a test liquid (E.sub.a), which can be further expressed as
E.sub.a=r.sub.pγ.sub.pl+γ.sub.1 (1)
Where γ.sub.pl is the interfacial tension between the particle and the test liquid, and γ.sub.l is the surface tension of the test liquid. The second configuration is that the particle surface is completely wetted by a lubricant oil (E.sub.b), namely,
E.sub.v=r.sub.pγ.sub.po+γ.sub.o (2)
where γ.sub.po is the interfacial tension between the particle and the lubricant oil, and γ.sub.o is the surface tension of the lubricant oil. The third wetting configuration is where the particle surface is completely wetted by a lubricant oil with a test liquid floating on top of it (E.sub.c), derived as,
E.sub.c=r.sub.pγ.sub.po+γ.sub.ol+γ.sub.l (1)
where γ.sub.ol is the interfacial tension between the lubricant oil and the test liquid.
[0043] Substituting the Young equation γ.sub.p=γ.sub.pl+γ.sub.1 cos θ.sub.pl into equation (1) yields the following equation of E.sub.a,
E.sub.a=r.sub.p(γ.sub.p−γ.sub.l cos θ.sub.pl)+γ.sub.l (4)
where γ.sub.p is the surface tension of the particle, and θ.sub.pl is the intrinsic contact angle of the test liquid on a flat surface made of the particle material. Similarly, by substituting the Young equation γ.sub.p=γ.sub.po+γ.sub.o cos θ.sub.po into equations S2 and S3, yields
E.sub.v=r.sub.p(γ.sub.p−γ.sub.o cos θ.sub.po)+γ.sub.o (5)
E.sub.c=r.sub.p(γ.sub.p−γ.sub.o cos θ.sub.po)+γ.sub.ol+γ.sub.l (6)
where θ.sub.po is the intrinsic contact angle of the lubricant oil on a flat surface of the particle material.
[0044] To create a colloid film, in which the particle are not replaced by the test liquid, E.sub.a should be always larger than E.sub.b and E.sub.c. Thus, ΔE.sub.1=E.sub.a−E.sub.b>0 and ΔE.sub.2=E.sub.a−E.sub.c>0. After substituting equations (4), (5) and (6), leads to
ΔE.sub.1=E.sub.a−E.sub.b=r.sub.p(γ.sub.o cos θ.sub.po−γ.sub.l cos θ.sub.pl)+γ.sub.l−γ.sub.o>0 (7)
ΔE.sub.2=E.sub.a−E.sub.c=r.sub.p(γ.sub.o cos θ.sub.po−γ.sub.l cos θ.sub.pl)−γ.sub.ol>0 (8)
Therefore, satisfying the interfacial energy conditions (7) and (8) meets the second criterion to form a stable colloid film to repel the external immiscible liquids. The colloidal particles' affinity ensures the stability of the colloid to the repelled liquid, as shown in
[0045] To ensure that the colloid film must stably adhere to the smooth solid, the interaction between the colloid and the smooth solid is considered. The smooth solid must be preferentially wetted by the colloid rather than by the tested liquid. Thus, the interfacial energies of smooth solids completely wetted by a test liquid (E.sub.d) or a lubricant oil (E.sub.e), expressed as,
E.sub.d=γ.sub.sl+γ.sub.l (9)
E.sub.e=γ.sub.sc+γ.sub.c (10)
where γ.sub.c is the surface tension of the colloid, is the interfacial tension between the smooth solid and the test liquid, and γ.sub.sc is the interfacial tension between the smooth solid and the colloid. By substituting the Young equations γ.sub.s=γ.sub.sl+γ.sub.1 cos θ.sub.sl and γ.sub.s=γ.sub.sc+γ.sub.c cos θ.sub.sc, it can be deduced that
E.sub.d=γ.sub.s−γ.sub.l cos θ.sub.sl+γ.sub.l (10)
E.sub.e=γ.sub.s−γ.sub.c cos θ.sub.sc+γ.sub.c (11)
where γ.sub.s is the surface tension of the smooth solid, and θ.sub.sc and θ.sub.sl are the intrinsic contact angles of the colloid and the test liquid on the smooth solid. To ensure that the smooth solid is preferentially wetted by the colloid rather than the test liquid, E.sub.d should be larger than E.sub.e, that is,
ΔE.sub.3=E.sub.d−E.sub.e=γ.sub.c cos θ.sub.sc−γ.sub.l cos θ.sub.sl+γ.sub.l−γ.sub.c>0 (12)
[0046] Taken together, ΔE.sub.1>0, ΔE.sub.2>0, and ΔE.sub.3>0, must be simultaneously satisfied to create a stable CISS. If one of these conditions is not satisfied, the test liquid will not be repelled by the colloid. The colloid film should have a preferred affinity to adhere to smooth solids stably to form a mobile particle roughness and not be displaced by the repelled liquid at the surface, as illustrated in
[0047] In an embodiment, the CISS can repel all states of matter: liquids, solids, and gas bubbles. In an exemplary embodiment, a stable colloid suspension is formed by inclusion of low-surface-energy polytetrafluoroethylene (PTFE) microparticles, as shown in
[0048] The designed CISS exhibits exceptional liquid repellency as evidenced by extremely low contact angle hysteresis Δθ<3.0°, as shown pictorially for the repelled liquid hexane in
TABLE-US-00001 TABLE 1 Comparison of the experimental results and theoretical design criteria to create stable CISS. Test Stable CISS Solid liquid Colloid r.sub.p γ.sub.o γ.sub.l γ.sub.ol γ.sub.c θ.sub.po θ.sub.pl θ.sub.sc θ.sub.sl ΔE.sub.1 ΔE.sub.2 ΔE.sub.3 The Exp S. Al Hexadecane PTFE 3.69 17.81 27.47 9.86 17.84 5.0 70.9 10.0 59.4 42.0 22.4 13.2 Y/Y/Y Y S. Al Dodecane ϕ = 0.01 3.69 17.81 25.35 7.75 17.84 5.0 62.6 10.0 52.5 30.0 14.7 9.6 Y/Y/Y Y S. Al Decane 3.69 17.81 23.83 6.55 17.84 5.0 50.0 10.0 47.0 15.0 2.4 7.3 Y/Y/Y Y S. Al Ethanol 3.69 17.81 22.1 10.01 17.84 5.0 60.5 10.0 37.1 29.6 15.3 4.2 Y/Y/Y Y S. Al Octane 3.69 17.81 21.62 4.84 17.84 5.0 44.7 10.0 33.9 12.6 3.9 3.4 Y/Y/Y Y S. Al Heptane 3.69 17.81 20.14 3.66 17.84 5.0 42.5 10.0 30.4 13.0 7.0 2.5 Y/Y/Y Y S. Al Hexane 3.69 17.81 18.43 2.17 17.84 5.0 31.5 10.0 25.1 8.1 5.3 1.5 Y/Y/Y Y S. Al Hexadecane PTFE 8.26 17.81 27.47 9.86 17.96 5.0 70.9 10.0 59.4 82.0 62.4 13.2 Y/Y/Y Y S. Al Dodecane ϕ = 0.02 8.26 17.81 25.35 7.75 17.96 5.0 62.6 10.0 52.5 57.7 42.4 9.6 Y/Y/Y Y S. Al Decane 8.26 17.81 23.83 6.55 17.96 5.0 50.0 10.0 47.0 26.0 13.5 7.3 Y/Y/Y Y S. Al Ethanol 8.26 17.81 22.1 10.01 17.96 5.0 60.5 10.0 37.1 61.0 46.7 4.2 Y/Y/Y Y S. Al Octane 8.26 17.81 21.62 4.84 17.96 5.0 44.7 10.0 33.9 23.4 14.8 3.4 Y/Y/Y Y S. Al Heptane 8.26 17.81 20.14 3.66 17.96 5.0 42.5 10.0 30.4 26.2 20.2 2.5 Y/Y/Y Y S. Al Hexane 8.26 17.81 18.43 2.17 17.96 5.0 31.5 10.0 25.1 17.4 14.6 1.5 Y/Y/Y Y U. Al Hexadecane PTFE 3.69 17.81 27.47 9.86 17.84 5.0 70.9 20.9 14.7 42.0 22.4 −0.3 Y/Y/N N U. Al Dodecane ϕ = 0.01 3.69 17.81 25.35 7.75 17.84 5.0 62.6 20.9 7.2 30.0 14.7 −1.0 Y/Y/N N U. Al Decane 3.69 17.81 23.83 6.55 17.84 5.0 50.0 20.9 5.0 15.0 2.4 −1.1 Y/Y/N N U. Al Ethanol 3.69 17.81 22.1 10.01 17.84 5.0 60.5 20.9 5.0 29.6 15.3 −1.1 Y/Y/N N U. Al Octane 3.69 17.81 21.62 4.84 17.84 5.0 44.7 20.9 5.0 12.6 3.9 −1.1 Y/Y/N N U. Al Heptane 3.69 17.81 20.14 3.66 17.84 5.0 42.5 20.9 0.0 13.0 7.0 −1.2 Y/Y/N N U. Al Hexane 3.69 17.81 18.43 2.17 17.84 5.0 31.5 20.9 0.0 8.1 5.3 −1.2 Y/Y/N N U. Al Hexadecane PTFE 8.26 17.81 27.47 9.86 17.96 5.0 70.9 21.7 14.7 82.0 62.4 −0.4 Y/Y/N N U. Al Dodecane ϕ = 0.02 8.26 17.81 25.35 7.75 17.96 5.0 62.6 21.7 7.2 57.7 42.4 −1.1 Y/Y/N N U. Al Decane 8.26 17.81 23.83 6.55 17.96 5.0 50.0 21.7 5.0 26.0 13.5 −1.2 Y/Y/N N U. Al Ethanol 8.26 17.81 22.1 10.01 17.96 5.0 60.5 21.7 5.0 61.0 46.7 −1.2 Y/Y/N N U. Al Octane 8.26 17.81 21.62 4.84 17.96 5.0 44.7 21.7 5.0 23.4 14.8 −1.2 Y/Y/N N U. Al Heptane 8.26 17.81 20.14 3.66 17.96 5.0 42.5 21.7 0.0 26.2 20.2 −1.3 Y/Y/N N U. Al Hexane 8.26 17.81 18.43 2.17 17.96 5.0 31.5 21.7 0.0 17.4 14.6 −1.3 Y/Y/N N S. Al Hexadecane Silica 6.19 17.81 27.47 9.86 18.70 33.7 41.5 8.4 59.4 −26.0 −45.5 13.3 N/N/Y N S. Al Dodecane ϕ = 0.01 6.19 17.81 25.35 7.75 18.70 33.7 36.2 8.4 52.5 −27.4 −42.7 9.7 N/N/Y N S. Al Decane 6.19 17.81 23.83 6.55 18.70 33.7 27.5 8.4 47.0 −33.1 −45.7 7.4 N/N/Y N S. Al Ethanol 6.19 17.81 22.1 10.01 18.70 33.7 36.2 8.4 37.1 −14.4 −28.7 4.3 N/N/Y N S. Al Octane 6.19 17.81 21.62 4.84 18.70 33.7 17.6 8.4 33.9 −32.0 −40.7 3.5 N/N/Y N S. Al Heptane 6.19 17.81 20.14 3.66 18.70 33.7 7.3 8.4 30.4 −29.6 −35.6 2.6 N/N/Y N S. Al Hexane 6.19 17.81 18.43 2.17 18.70 33.7 5.2 8.4 25.1 −21.3 −24.1 1.5 N/N/Y N U. Al Hexadecane Silica 6.19 17.81 27.47 9.86 18.70 33.7 41.5 28.2 14.7 −26.0 −45.5 −1.3 N/N/N N U. Al Dodecane ϕ = 0.01 6.19 17.81 25.35 7.75 18.70 33.7 36.2 28.2 7.2 −27.4 −42.7 −2.0 N/N/N N U. Al Decane 6.19 17.81 23.83 6.55 18.70 33.7 27.5 28.2 5.0 −33.1 −45.7 −2.1 N/N/N N U. Al Ethanol 6.19 17.81 22.1 10.01 18.70 33.7 36.2 28.2 5.0 −14.4 −28.7 −2.1 N/N/N N U. Al Octane 6.19 17.81 21.62 4.84 18.70 33.7 17.6 28.2 5.0 −32.0 −40.7 −2.1 N/N/N N U. Al Heptane 6.19 17.81 20.14 3.66 18.70 33.7 7.3 28.2 0.0 −29.6 −35.6 −2.2 N/N/N N U. Al Hexane 6.19 17.81 18.43 2.17 18.70 33.7 5.2 28.2 0.0 −21.3 −24.1 −2.2 N/N/N N
“S. Al” and “U. Al” indicate the silanized and untreated smooth aluminum substrates. “Y” and “N” in theoretical column (“The.”) represent whether the corresponding criterion is satisfied or not. For example, “Y/Y/Y” indicates three criteria are all satisfied, that is, ΔE.sub.1>0, ΔE.sub.2>0, and ΔE.sub.3>0, while “Y/Y/N” indicates ΔE.sub.1>0, ΔE.sub.2>0, and ΔE.sub.3<0. “Y” in experimental column (“Exp.”) indicates the designed CISS is stable, while “N” indicates the CISS is not stable, where the colloid is replaced by the test liquid. Φ is the mass fraction, r.sub.p is the roughness factor, γ.sub.o is the surface tension of the lubricant oil (see Table 2, below), γ.sub.l is the surface tension of the used test liquids (see Table 3, below), γ.sub.ol is the interfacial tension between the lubricant oil and the test liquids (see Table 4, below), and θ.sub.po, θ.sub.pl, θ.sub.sc and θ.sub.sl are the intrinsic contact angles of the lubricant oil on a flat particle surface, the test liquid on a flat particle surface, the colloid on a smooth solid, and the test liquid on a smooth solid (see Table 5, below).
TABLE-US-00002 TABLE 2 Physical and chemical properties of the lubricant oils. Surface Dynamic tension viscosity Chemical Name (mN/m) (mPa .Math. s) Source &Grade Perfluorotripentylamine 17.81 ± 0.07 .sup.a 22.27 ± 0.47 .sup.b Aladdin (FC-70) (used in density gradient studies) Krytox GPL 101 16-20 .sup.b 17.4 .sup.b Dupont ™ Krytox ® Krytox GPL 103 16-20 .sup.b 82 .sup.b Dupont ™ Krytox ® Note: Properties were collected at 20° C. unless otherwise specified as superscript. Reference sources: .sup.(a) surface tension and viscosity were obtained from five independent measurements at ambient conditions; .sup.(b) manufacturer specifications.
TABLE-US-00003 TABLE 3 Surface tension of the tested liquids repelled by the CISS. Surface tension Name (mN/m) Chemical Source &Grade Hexane 18.43 .sup.b J&K Scientific (97.5%) Heptane 20.14 .sup.b Aladdin (>99.5%) Octane 21.62 .sup.b Aladdin (>99%) Ethanol 22.10 .sup.b VWR International (99.95%) Decane 23.83 .sup.b Aladdin (>99%) Dodecane 25.35 .sup.b Aladdin (>99%) Hexadecane 27.47 .sup.b Aladdin (98%) Mineral oil 30.45 ± 0.03 .sup.a Sigma-Aldrich (Light oil) N, N-dimethyl 37.10 b J&K Scientific (≥99.9%) formamide (DMF) Ethylene glycol 47.70 .sup.b Aladdin (>99%) Glycerol 64.00 .sup.b Sigma-Aldrich (≥99.5%) Deionized water 72.80 .sup.b HKU Nanofluids Lab Note: Properties were: collected at 20° C. unless otherwise specified as superscript. Reference sources: .sup.(a) surface tension was calculated from five independent measurements by the Wilhelmy plate method at ambient conditions (22° C. to 25° C.); .sup.(b) DataPhysics (https://www.dataphysics-instruments.com/Downloads/Surface-Tensions-Energies.pdf).
TABLE-US-00004 TABLE 4 Measured interfacial tensions between FC-70 oil and various liquids. (1) Interfacial tension Liquid/liquid (mN/m) (2) FC-70/Hexadecane (3) 9.86 ± 0.39 (4) FC-70/Dodecane (5) 7.75 ± 0.43 (6) FC-70/Decane (7) 6.55 ± 0.26 (8) FC-70/Ethanol (9) 10.01 ± 0.19 (10) FC-70/Octane (11) 4.84 ± 0.09 (12) FC-70/Heptane (13) 3.66 ± 0.13 (14) FC-70/Hexane (15) 2.17 ± 0.14 Note: Interfacial tension measurements were performed by the pendant droplet method at ambient conditions (22° C. to 25° C.). These interfacial tensions were calculated from fifteen independent measurements.
TABLE-US-00005 TABLE 5 Measured roughness factor for the colloid on aluminum substrate. Colloid Roughness factor PTFE + FC-70 (ϕ = 0.01) 3.69 ± 0.39 PTFE + FC-70 ( ϕ = 0.02) 8.26 ± 0.55 Silica + FC-70 (ϕ = 0.01) 6.19 ± 0.53 Note: Roughness factors were measured at ambient conditions (22° C. to 25° C.), and calculated from five independent measurements.
TABLE-US-00006 TABLE 6 Viscosity of the tested liquids repelled by the CISS. Name Dynamic viscosity (Pa .Math. s) Chemical Source &Grade Hexane 0.0003 .sup.a J&K Scientific (97.5%) Deionized water 0.00089 .sup.a HKU Nanofluids Lab Ethanol 0.001074 .sup.a VWR International (99.95%) Hexadecane 0.00303 .sup.a Aladdin (98%) Ethylene glycol 0.01606 .sup.a Aladdin (>99%) Silicone oil 0.02 .sup.b Aladdin PMX-200 Silicone oil 0.1 .sup.b Aladdin PMX-200 Silicone oil 0.5 .sup.b Aladdin PMX-200 Glycerol 0.934 .sup.a Sigma-Aldrich (≥99.5%) Honey 5.26 ± 0.07 .sup.c BESTbuy Centifloral Honey Tomato ketchup 23.96 ± 0.18 .sup.c Delmonte Ketchup Toothpaste 163.65 ± 0.71 .sup.c Colgate Anticavity Toothpaste Peanut butter 228.72 ± 10.56 .sup.c Skippy Creamy Peanut Butter Note: Properties are collected at 25° C. unless otherwise specified as superscript. Reference sources: .sup.(a) CRC; .sup.(b) manufacturer specifications, .sup.(c) dynamic viscosity was calculated from five independent measurements tested by Brookfield rheometer at a speed of 0.1 rpm.
TABLE-US-00007 TABLE 7 Measured surface tensions for the colloid lubricants. Colloid Surface tension (mN/m) PTFE + FC-70 (ϕ = 0.01) 17.84 ± 0.04 PTFE + FC-70 (ϕ = 0.02) 17.96 ± 0.08 Silica + FC-70 (ϕ = 0.01) 18.70 ± 0.04 calculated from five independent measurements by the Wilhelmy plate method at ambient conditions (22° C. to 25° C.).
[0049] In addition to repelled fluids, the CISS resists adhesion of viscoelastic solids, as shown in
[0050]
[0051] The particle fraction in the colloid mediates repellency dynamics. This is indicated by the slippery behaviors of three types of fluid droplets on CISSs having colloids with different mass fractions, ϕ, of particles. In
F.sub.d≈mg sin α≈2πRγ.sub.l(cos θ.sub.r−cos θ.sub.a) (4)
[0052] where m is the weight of the droplet, g is the gravitational acceleration, R is the droplet base radius, and θ.sub.a and θ.sub.r are the advancing and receding contact angles, respectively. Quantification of the dissipative force, F.sub.d, acting on a moving droplet can be measure at a constant speed using a cantilever force sensor. As displayed in
[0053] For a moving droplet on a CISS, the dissipative force F.sub.d on the CISS can be quantified by integrating the viscous stress ηU/h over the area 2πRl, where η is the colloid viscosity, U is the constant speed of the droplet, h is the thickness of the colloid film, and l is the area size of capillary pressure flow at the rim around the droplet base. Since the formation of the colloid film follows the Landau-Levich-Derjaguin law, where l˜RCa.sup.1/3 and h˜RCa.sup.2/3, the dissipative force F.sub.d on the CISS can be estimated as
F.sub.d≈2πRγ.sub.lcCa.sup.2/3 (5)
[0054] Where Ca=ηU/γ.sub.lc is the capillary number, and γ.sub.lc is the interfacial tension between the colloid and the test liquid. Such scaling of F.sub.d is indicated in
[0055] The long-term stability of the CISS can be mediated by the particle fraction of the colloid, as indicated by droplet impacting test on the CISS surfaces with different mass fraction, ϕ. When ϕ is smaller than 0.01, the colloid film on the CISS can be broken down by the impinging droplets. However, when ϕ≥0.01, the colloid film forms a stabilized CISS under continuous droplet impacting, which is the same as that observed with a SLIPS, as indicated in
[0056] CISSs are successfully fabricated on various materials with roughness factors from 1.00 to 1.45 including metals (aluminum, stainless steel, copper, titanium, nickel, and magnesium alloy), silicon, ceramics, and plastics (PTFE, FEP, PFA and ABS). These CISS surfaces exhibit superior repellency against mineral oil, water, tomato ketchup and peanut butter, as shown in
[0057] Although, as described herein with perfluorinated fluid, such as, but not limited to perfluorotripentylamine (FC-70) and Krytox™ oils, the non-volatile lubricating fluid can be another liquids, such as silicone oils, mineral oils, ferrofluid, ionic liquid, polyalphaolefin oils, and hydroxy-terminated polydimethylsiloxanes for CISS surfaces that can be paired to repelling of liquids and solids that are immiscible with the liquid and particles that have a high affinity to the non-volatile lubricating fluid over any material to be repelled. The nanoparticles and/or microparticles can be waxes, silica, titanium oxide, silver, and graphene, which have, or can be surface functionalized to have a preferred affinity for the lubricating fluid over the material that is to be repelled. The surface of the nanoparticles and/or microparticles can be treated with a silylating agent, a functional trialkoxylsilane, trichlorosilane, silazane, or other silylating reagent, to bond a functional group to the surface that provides a particle's surface with affinity to the lubricating fluid but not the liquid to be repelled. The CISS surface is repellant to all fluids that are not miscible with the lubricating fluid. For example, the silicone or hydrocarbon oil can repel aqueous solutions or ice. As shown in
[0058] The CISS shows superior self-healing after various mechanical damage to the surface including wiping, touching, tape peeling, blade scratching, and sandpaper wearing, benefiting from an intelligent self-built roughness of the colloid. Unlike state of the art repellent surface that are predesigned with fixed surface structures, the particle-enabled roughness within the colloid are intrinsically movable. Therefore, the colloid film flows into the damage area on the smooth solid by capillary or gravity action to restore the damaged colloid film. As shown in
[0059] In addition to superior resistance to mechanical damage, the CISS is endowed with an excellent resistance to chemical damage. The chemical resistance is indicated by the stable repellency to droplets at different pH values, as shown in
[0060] The stability of CISS remains with little change after continuous droplet impact on the inclined CISS which is similar to that of for SLIPS,
[0061] Hence, in embodiments of invention, stable matter-repellent slippery surfaces are prepared on smooth solids by coating a colloid suspension consisting of a lubricant oil and functional microparticles. The slippery coatings do not require structured substrate surfaces or deposition of auxiliary layers to entrench a thin lubricant film, rather the colloid is a self-stabilized lubricating film without aid of structural roughness planarizes to a smooth surface with exceptional repellency against all states of matter, including bubbles, fluids, viscoelastic solids, and solid ice. Different from the monotonous repellency to single-phase foulant on the previous liquid-repellent surfaces, such comprehensive repellency to foulants with different phases allows our CISS to normally work under extreme conditions that simultaneous results in contamination from materials in multiple states of matter. Various smooth substrates that can be employed to form CISSs including metals, silicon, glass, ceramics, and plastics. In addition to open surfaces, CISSs can be formed on the surfaces of closed spaces, including bottles and catheters, since there is no need to generate structural roughness on closed surfaces in advance. These advantages enable a wide range of promising applications as exemplified by slippery vials for preventing food adhesion and slippery catheters for contamination-free fluid navigation.
[0062] It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application. In addition, any elements or limitations of any invention or embodiment thereof disclosed herein can be combined with any and/or all other elements or limitations (individually or in any combination) or any other invention or embodiment thereof disclosed herein, and all such combinations are contemplated with the scope of the invention without limitation thereto.
Materials and Methods
[0063] Synthesis of Colloid Lubricants
[0064] PTFE microparticles were added into low-surface-tension perfluorinated oils, including FC-70 and Chemours™ Krytox™ oils, at specific mass fractions. The suspensions were subsequently exposed to ultrasound sonication for 1 hour and magnetic stirring for 2 hours to create a stable colloid suspension.
[0065] Preparation of CISS
[0066] To enhance the affinity between the colloid and smooth solid substrates, the solid surfaces, including aluminum, stainless steel, copper, silicon, titanium, nickel, magnesium alloy, ceramics, ABS, and glass vials, were silylated by immersing the substrate in a 1 mM ethanol solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane for about six hours, followed by heat treatment at 80° C. in air for one hour. The colloid was fully infused on these solid surfaces by capillary wetting or spraying. Excess lubrication film was drained from the smooth surface for 30 minutes via gravity. Unless otherwise specified, the colloid suspension consist of FC-70 oil and PTFE microparticles with a mass fraction of 0.02 was used throughout experiments.
[0067] Preparation of Superhydrophobic Surface and SLIPS
[0068] Superhydrophobic Surface was fabricated by etching the aluminum sample in a 2 mol/1 hydrochloric acid solution for 40 minutes, followed by the ultrasonic cleaning in deionized water for 2 minutes. To render it superhydrophobic, the etched aluminum was first modified by immersion in a 1 mM ethanol solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane for 2 hours, and subsequently heated at 100° C. in air for 30 minutes. To prepare the SLIPS, the superhydrophobic surface was fully infused with the FC-70 oil. The excess oil was drained for 30 minutes via gravity.
[0069] Topography characterization Functional PTFE and silica particles in the colloids were imaged by using a transmission electron microscopy (Philips CM100). The topography of PTFE particles and the superhydrophobic surface were characterized using a scanning electron microscopy (Hitachi S4800). The roughness factors of various smooth surfaces, superhydrophobic surface, and PTFE particle surfaces were determined by a laser profilometer (Bruker ContourGT-K1).
[0070] Wettability and Repellency Measurements
[0071] Contact angles of various fluid and colloid droplets (˜5 μl) on untreated and silylated aluminum surfaces, flat PTFE surface, flat silica surface, and superhydrophobic surface were measured with a contact angle goniometer (Dataphysics OCA 25) at ambient conditions (22° C.-25° C.). To measure sliding angles, CISS surfaces were tilted with respect to the horizontal plane until the fluid droplets or viscoelastic peanut butter (˜5 μl) start to slide along the surfaces. After recording the sliding behaviors of different fluid droplets, the advancing and receding contact angles of these fluids on the CISS were measured by the OCA 25 goniometer. The contact angle hysteresis was calculated by subtracting the receding contact angle by the advancing contact angle. The surface tensions of the colloids and FC-70 oil were evaluated using a dynamic contact angle tensiometer (Dataphysics DACT 25) by the Wilhelmy plate method. The interfacial tensions between the FC-70 and various fluids were measured based on the pendant droplet method at ambient conditions by using the OCA 25 goniometer.
[0072] Dynamic Viscosity Measurement
[0073] The dynamic viscosities of the FC-70 oil and various colloids were measured by a viscometer (Brookfield DV-II+ Pro) equipped with a CPE-42 spindle. The dynamic viscosities of honey, tomato ketchup, toothpaste, and peanut butter were measured by a rheometer (Brookfield R/S) at a set speed of 0.1 rpm.
[0074] Droplet Impact Test
[0075] To investigate the stability of CISS, continuous droplet impact test was performed on three surfaces, including CISS, SLIPS, and smooth surface infused by the FC-70 oil. These surfaces were tilted at an angle of about 10°, and were continuously impacted by falling water droplets (˜25 μl) from a specific height of 10 cm. The falling rate of water droplets was controlled by a syringe pump (LongerPump LSP01-2A). The droplet impacting behavior was captured by a high-speed camera (iX Cameras, iSpeed 510) at a frame rate of 5000 fps. The stabilities of these surfaces were evaluated by varying the sliding angle after the droplet impact.
[0076] Bubble Repellency Test
[0077] Bubble repellency tests were carried out under deionized water at a depth of about 1 cm. Air bubbles (˜30 μl) were generated release from a pipette on the smooth surface and CISS surface, both of which were inclined at about 2.5°. The sliding processes of air bubbles on these surfaces were captured by the high-speed camera (iX Cameras, iSpeed 510).
[0078] Ice Repellency Test
[0079] Ice repellency tests were performed on CISS and smooth surfaces using a precisely controlled cooling device (Dataphysics TC 160Pro). Blue water droplets (˜25 μl) dyed by methylene blue were released on the CISS and smooth surfaces, which were placed on the horizontal cooling stage at a set temperature of −5° C. After cooling for about 1 minute, the cooling stage was tilted at an angle of ˜10°. The sliding behaviors of droplets on two surfaces were recorded by a digital camera (Canon EOS 600D).
[0080] Evaporation Test
[0081] The evaporation rate of three colloids synthesized by the FC-70, Krytox™ GPL 101 and Krytox™ GPL 103 oils were evaluated for thirty consecutive days in an open area at a relative humidity 50%-60% and a temperature of 22° C.-25° C. During these days, the mass of each CISS sample was monitored by a high-resolution balance (KERN AEJ 200-5CM) with a sensitivity of 0.1 mg, and the sliding angle of water droplet (˜5 μl) on each CISS sample was measured by the contact angle goniometer (Dataphysics OCA 25).
[0082] Dissipative Force Measurement
[0083] The dissipative force acting on a moving droplet on the CISS was measured by a built cantilever force sensor consisting of a capillary glass tube with a typical length of 8 cm, an inner diameter of 0.1 mm, and an outer diameter of 0.32 mm. The moving speed of the underlying CISS sample was precisely controlled by a motor stage (Aerotech PlanarDL-200XY). The deflection of capillary tube was optically captured by the high-speed camera (iX Cameras, iSpeed 510).
[0084] Adhesion Test and Visualization
[0085] Tomato ketchup, honey and yogurt samples were used to examine the adhesion of slippery and smooth glass vials. Each ˜40 ml sample was put into a slippery or smooth glass 50 ml vial, and the samples were poured out while optically recording the pour with a digital camera (Canon EOS 600D). The mass losses of the food from the vials were monitored by a high-resolution balance (KERN AEJ 200-5CM).
[0086] Slippery Catheter Test
[0087] A PTFE catheter with an inner diameter of 0.5 mm and an outer diameter of 0.9 mm was used to create a slippery CISS catheter. The sliding behaviors of mineral oil droplets stained by the oil red O on and inside the tilted slippery or smooth catheters (tilting angle ˜5°) were captured by the high-speed camera (iX Cameras, iSpeed 510).
[0088] All publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.
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