SLIPPERY SELF-LUBRICATING POLYMER SURFACES

• US 20150152270A1
• Filed: 07/12/2013
• Published: 06/04/2015
• Est. Priority Date: 07/12/2012
• Status: Active Grant

• Current Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Original Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Inventors: Aizenberg, Joanna, Aizenberg, Michael, Kim, Philseok, Wong, Tak Sing, Cui, Jiaxi, Dunn, Stuart, Hatton, Benjamin, Howell, Caitlin, Yao, Xi
• Granted Patent: US 9,963,597 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: A61L 2400/10 Materials for lubricating medical devices
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/14 Materials characterised by their function or physical properties , e.g. lubricating compositions
• CPC Class Codes: A61L 31/04 Macromolecular materials
• CPC Class Codes: A61L 31/049 Rubbers
• CPC Class Codes: A61L 31/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: B01D 2321/281 by applying a special coating to the membrane or to any module element
• CPC Class Codes: B01D 65/08 Prevention of membrane fouling or of concentration polarisation
• CPC Class Codes: B05D 5/08 to obtain an anti-friction or anti-adhesive surface rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30
• CPC Class Codes: B08B 17/025 Prevention of fouling with liquids by means of devices for containing or collecting said liquids
• CPC Class Codes: B08B 17/065 the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
• CPC Class Codes: C08J 2300/00 Characterised by the use of unspecified polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 201/005 Dendritic macromolecules
• CPC Class Codes: C09D 5/1637 Macromolecular compounds
• CPC Class Codes: C09D 5/1675 Polyorganosiloxane-containing compositions
• CPC Class Codes: C09D 5/1693 as part of a multilayer system
• CPC Class Codes: C10M 105/76 containing silicon
• CPC Class Codes: C10M 171/00 Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated chemically defined ingredients C10M101/00 - C10M169/00; petroleum fractions C10M101/02, C10M121/02, C10M159/04
• CPC Class Codes: C10M 2203/1006 : used as base material
• CPC Class Codes: C10M 2229/025 : used as base material
• CPC Class Codes: C10M 2229/0515 : used as base material
• CPC Class Codes: C10N 2050/14 : Composite materials or sliding materials in which lubricants are integrally molded
• CPC Class Codes: C10N 2070/00 : Specific manufacturing methods for lubricant compositions

Abstract

The present disclosure describes a strategy to create self-healing, slippery self-lubricating polymers. Lubricating liquids with affinities to polymers can be utilized to get absorbed within the polymer and form a lubricant layer (of the lubricating liquid) on the polymer. The lubricant layer can repel a wide range of materials, including simple and complex fluids (water, hydrocarbons, crude oil and bodily fluids), restore liquid-repellency after physical damage, and resist ice, microorganisms and insects adhesion. Some exemplary applications where self-lubricating polymers will be useful include energy-efficient, friction-reduction fluid handling and transportation, medical devices, anti-icing, optical sensing, and as self-cleaning, and anti-fouling materials operating in extreme environments.

Claims

1. An article having a slippery surface, the article comprising:

at least one surface comprising;

a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1; and

a lubricating liquid,

wherein the supramolecular polymer and the lubricating liquid have an affinity for each other such that the lubricating liquid is absorbed within the polymer material in an amount sufficient to form a slippery lubricating layer on a surface of the liquid-swollen polymer.

2. The article of claim 1, wherein the polymer P comprises an elastomer.

3. The article of claim 1, wherein the polymer P comprises silicone elastomers.

4. The article of claim 3, wherein the lubricating liquid comprises silicone oils.

5. The article of claim 1, wherein the polymer P comprises fluorosilicone elastomers.

6. The article of claim 5, wherein the lubricating liquid comprises perfluorocarbons.

7. The article of claim 1, wherein the polymer P comprises petroleum-based polymers.

8. The article of claim 7, wherein the lubricating liquid comprises hydrocarbons.

9. The article of claim 1, wherein polymer P can be a simple polymer or a polymer blend or block co-polymer.

10. The article of claims 1-9, wherein the supramolecular block is selected from non-covalent blocks that provide one or more of host-guest interaction, coordination, π

-π

interactions, and hydrogen bonding with each other or with the polymer.

11. The article of claim 1, wherein x and y are selected to provide a predetermined swelling ratio, wherein the swelling ratio is the ratio of the weight or volume of supramolecular polymer with and without lubricating liquid.

12. The article of claim 1, wherein x and y are selected to provide a predetermined mechanical property of the supramolecular polymer.

13. The article of claim 1, wherein the wt/wt ratio of supramolecular polymer and the lubricating liquid ranges from 10:

1 to 1;

10.

14. The article of claim 1, wherein the wt/wt ratio of supramolecular polymer and the lubricating liquid ranges from 4:

1 to 1;

4.

15. The article of claim 1, wherein the wt/wt ratio of supramolecular polymer and the lubricating liquid ranges from 2:

1 to 1;

2.

16. The article of claim 1, wherein the lubricating liquid-swollen polymer material comprises an excess of lubricating liquid and the excess lubricating liquid is localized in lubricating liquid-rich domains with the polymer material.

17. The article of claim 16, wherein the lubricating liquid-rich domains are a reservoir for lubricating liquid.

18. The article of claim 1, wherein the absorbed lubricating liquid is a reservoir for liquids.

19. The article of claim 1, wherein the lubricating liquid comprises two or more lubricating liquids.

20. The article of claim 19, wherein a first lubricating liquid has a lower viscosity than a second lubricating liquid and the second lubricating liquid has a lower vapor pressure than the first lubricating liquid.

21. The article of claim 1, wherein the lubricating liquid is non-toxic.

22. The article of claim 1, wherein the lubricating liquid further is selected for its immiscibility and unreactivity with a predetermined material to be repelled from the surface.

23. The article of claim 22, wherein the predetermined material is a biological material.

24. The article of claim 1, wherein the lubricating liquid further is selected to have low vapor pressure and/or low viscosity.

25. The article of any of the preceding claims, wherein the article comprises a roughened surface.

26. The article of claim 25, wherein the lubricant layer forms a conformal layer with the roughened surface.

27. The article of claim 25, wherein the lubricant layer forms flat layer over coating the roughened surface.

28. The article of claim 1, wherein the supramolecular polymer is combined with a fluidic network that can be infused with additional lubricating liquid to replenish the slippery layer on the surface.

29. The article of claim 28, wherein the supramolecular polymer is combined with a fluidic network comprising a coating that covers a surface.

30. The article of claim 28, wherein the supramolecular polymer comprising a fluidic network is a pipe container liner that covers its inner or outer surface.

31. The article of any of the preceding claims in which the surface comprises a coating layer on an article.

32. The article of claim 31, wherein the coating comprises two or more layers of lubricating liquid-swollen polymer.

33. The article of claim 32, wherein two or more layers of lubricating liquid-swollen polymer have different properties and/or compositions and are disposed on top of each other to provide a complex, programmable coating.

34. The article of any preceding claim, wherein the article is selected from containers, medical gloves, membranes, filters, pipes, tubing, wires, construction, materials, road signs or vehicles.

35. A method of reducing adhesion of a foreign material to an article, comprising:

providing an article having a slippery surfaces article comprising at least one surface comprising a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1; and

a lubricating liquid, according to any one of claims 1-34; and

contacting the article with a medium containing a foreign material, wherein the adhesion of the foreign material to the article is less than the adhesion of the foreign material to the article in the absence of the lubricating liquid.

36. The method of claim 35, wherein the supramolecular polymer maintains a layer of the absorbed lubricating liquid, or a liquid-polymer composite overlayer, or a conformally-coated lubricating liquid layer, at the surface of the polymer material.

37. The method of claim 35, wherein after physical damage affects a thickness of the lubricating layer, equilibrium between the lubricating liquid and the polymer material causes the lubricating layer to substantially return to the predamage thickness.

38. The method of claim 35, wherein the lubricating liquid is selected based on a surface tension of the lubricating liquid, an immiscibility and unreactivity of the lubricating liquid with the foreign material, a viscosity of the lubricating liquid, a melting temperature of the lubricating liquid, phase change temperature of the lubricating liquid, a vapor pressure of the lubricating liquid or any combination thereof.

39. The method of claim 35, wherein the foreign material is a fluid.

40. The method of claim 35, wherein the foreign material is a solid, such as ice.

41. The method of claim 35, wherein the foreign material is a biological material (biomolecules, cells, bodily fluids, microbes, algae, etc.).

42. The method of claim 35, wherein the foreign body comprises a fluid containing a colonizable cell.

43. The method of claim 35, wherein the supramolecular polymer is coated or applied onto a substrate selected from organic or inorganic materials, such as polymers, glasses, metals, oxides, nitrides, ceramics, cellulose (paper) or any combination thereof.

44. The method of claim 35, wherein the medium moves over the surface of the article.

45. The method of claim 35, wherein the medium is in static contact with the article.

46. The method of claim 35, wherein the article comprises:

a) a conduit, pipe or tube, wherein the slippery surface covers an inner and/or outer surface, the slippery surface comprising a lubricating layer or a liquid-polymer composite overlayer;

or

b) a gasket, wherein the lubricating liquid substantially covers an exterior surface of the gasket to form a lubricating layer over the exterior surface, or forms a liquid-polymer composite overlayer at the exterior surface of the gasket;

or

c) a membrane having a plurality of through holes, each said through hole open to the passage of liquid or gas there through, wherein the membrane is swollen with the lubricating liquid;

or

d) catheters, or

e) polymers with an integrated fluidic network for introduction of additional lubricant that can be in the form of biofuel release trays, injectable catheters or replenishable containers;

or

f) self-regulated pipes

47. The method of claim 35, wherein a greater than 70%, or greater than 80% or greater than 90% or greater than 95% or 99% reduction of biofilm formation is observed on the slippery surface after one hour, or 2 hours, or 8 hours, or 1 day, or 2 days, or 5 days, or one week, or one month, under dynamic flow.

48. The method of claim 35, wherein less than less than 40% or less than 30% or less than 20% or less than 15% or less than 10% or less than 5% surface coverage of the slippery surface by a colonizable cell or microorganism is observed on the slippery surface after 1 day or 2 days or 5 days or 1 week or 2 weeks or 16 days under static exposure.

49. A method of controlling the diameter and pressure drop in a fluid conduit comprising:

providing a conduit that is at least partially lined with a slippery layer having a first thickness, said slippery layer comprising a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1, and a lubricating liquid, wherein the supramolecular polymer and the lubricating liquid have an affinity for each other such that the lubricating liquid is absorbed within the polymer material in an amount sufficient to form a slippery layer on a surface of the lubricating liquid-swollen polymer,

flowing a fluid through the conduit, wherein the thickness of the slippery layer increases or decreases over time, as the slippery layer takes up or loses lubricant, wherein the diameter and pressure drop across the diameter can be controlled within a predetermined value.

50. A method of removing a deposit from a surface comprising:

providing a surface that is at least partially covered with a slippery layer, said slippery layer comprising a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1, and a lubricating liquid, wherein the supramolecular polymer and the lubricating liquid have an affinity for each other such that the lubricating liquid is absorbed within the polymer material in an amount sufficient to form a slippery layer on a surface of the lubricating liquid-swollen polymer,

wherein the slippery layer includes a network of fluidic channels disposed throughout the layer, said fluidic channels having an inlet port;

introducing a lubricating liquid into the fluidic channels through the inlet port, wherein the lubricating liquid is taken up by the supramolecular polymer and the slippery surface is provided with additional lubricating liquid that reduces the adhesion of a deposit from the surface.

51. The method of claim 50, further comprising washing the surface to remove the deposit having a reduced adhesion to the surface.

52. A method or preventing migration of microorganisms, comprising:

providing a barrier proximal to an area to which is it desired to prevent microorganism migration, said barrier comprising a slippery layer, said slippery layer comprising a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1, and a lubricating liquid, wherein the supramolecular polymer and the lubricating liquid have an affinity for each other such that the lubricating liquid is absorbed within the polymer material in an amount sufficient to form a slippery layer on a surface of the lubricating liquid-swollen polymer.

53. A method of forming a repellent, non-adhering, self-cleaning, and low friction surface comprising;

applying a flowable precursor composition comprising a curable polymer onto a surface; and

initiating curing of the polymer to form a cured polymer; and

before or after curing, incorporating a lubricating liquid into the flowable precursor composition, wherein the lubricating liquid and cured polymer together form a coating of lubricating liquid stabilized on or in the cured polymer.

54. The method of claim 53, wherein the cured polymer is a supramolecular polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is supramolecular blocks within this polymer network, wherein x+y=1 and “

y”

can be from 0 to 1.

55. The method of claim 53, wherein the flowable precursor composition is applied to a surface using a technique selected from a group consisting of spray painting, dip coating, spin coating, screen printing, stamping, flow coating, inkjet printing, 3D printing, or writing with a pen.

56. The method of claim 53, wherein the surface of the opposite side has an adhesive material.

57. The method of claim 53, wherein the surface is a roughened surface and the flowable precursor composition is applied at a thickness covering the underlying surface roughness and form a flat overcoating surface.

58. The method of claim 53, wherein the surface is a roughened surface and the flowable precursor composition is applied at a thickness forming a conformal layer following the topography of the roughened surface.

59. The method of claim 53, wherein incorporating a lubricating liquid occurs after curing of the polymer precursor.

60. The method of claim 59, further comprising functionalizing the surface of the cured polymer to provide surface having affinity with the lubricating liquid prior to incorporating a lubricating liquid.

61. The method of claim 53, wherein the surface is chemically functionalized or activated to provide adhesion with the cured polymer.

62. The method of claim 53, wherein the lubricating liquid stabilized on or in the cured polymer is selected to be repellent to aqueous liquids.

63. The method of claim 53, wherein the lubricating liquid stabilized on or in the cured polymer is selected to be repellent to organic liquids.

64. The method of claim 53, wherein the flowable precursor composition is applied in a continuous process.

65. The method of claim 53, wherein the surface is an adhesive backed surface.

66. A system for use in the formation of a repellent, non-adhering, self-cleaning, and low-friction surface, comprising:

a flowable precursor composition comprising a curable prepolymer, said composition capable of application as a coating over a large surface area;

a lubricating liquid that is capable of forming a coating with the hardened precursor composition, wherein the lubricating liquid and hardened polymer together form a coating of lubricating liquid stabilized on or in the hardened polymer; and

instructions for applying the precursor composition onto a surface for the purpose of obtaining a repellant, non-adhering, self-cleaning, and/or low-friction surface.

67. The system of claim 66, wherein the prepolymer comprises a perfluoroalkyl monomer or oligomer.

68. The system of claim 66, wherein the curing agent is selected from ultraviolet energy-activated, chemically-activated, thermal energy-activated, and moisture-activated curing agents.

69. The system of claim 66, wherein the lubricant is selected from the group consisting of fluorinated lubricants (liquids or oils), silicones, mineral oil, plant oil, water (or aqueous solutions including physiologically compatible solutions), ionic liquids, polyalpha-olefins (PAO), synthetic esters, polyalkylene glycols (PAG), phosphate esters, alkylated naphthalenes (AN) and silicate esters.

70. The system of claim 66, wherein the precursor composition or the lubricant further comprises one or more additives selected from the group consisting of small molecules or nanoparticle fillers, such as anti-oxidants, UV-stabilizers, foaming or anti-foaming agents, pigments, nucleating agents and fillers, to enhance mechanical properties or roughness, and to control optical properties or viscosity.

71. The system of claim 66, wherein lubricating agent is provided as a mixture with the precursor composition.

72. The system of claim 66, wherein lubricating agent is provided separate from the precursor composition.

73. The system of claim 72, wherein the instructions provide for the application of the lubricant after hardening of the precursor composition.

74. The system of claim 66, wherein the polymer precursor is selected to provide liquid crystalline properties when cured.

75. A membrane that is resistant to clogging and fouling, comprising:

a membrane comprising a swellable polymer and having at least one pore disposed through the thickness of the membrane, each said through pore open to the passage of liquid or gas there through; and

a first lubricating liquid having a first viscosity, said first lubricating liquid solubilized in at least an outer layer of the membrane including at least one pore to provide a lubricating layer.

76. The membrane of claim 75, further comprising:

a second lubricating liquid having a second viscosity, said second lubricating liquid forming a liquid layer on the lubricant swollen polymer of the membrane.

77. The membrane of claim 75, wherein the membrane is formed from a swellable polymer.

78. The membrane of claim 75, wherein the membrane comprises a coating comprising the swellable polymer.

79. The membrane of claim 75, wherein the pores comprise the openings/slits of the membrane filters on the order of 1 μ

m up to 1 mm in diameter.

80. The membrane of claim 75, wherein the second viscosity is greater than the first viscosity.