Slippery self-lubricating polymer surfaces

• US 9,963,597 B2
• Filed: 07/12/2013
• Issued: 05/08/2018
• 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, Cui, Jiaxi, Dunn, Stuart, Hatton, Benjamin, Howell, Caitlin, Kim, Philseok, Wong, Tak Sing, Yao, Xi
• Primary Examiner(s): Menon, Krishnan S
• Assistant Examiner(s): HUANG, RYAN
• Application Number:
  US14/414,291
• Publication Number:
  US 20150152270A1
• Time in Patent Office: 1,761 Days
• Field of Search: None
• 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 to repel target materials, the article comprising:

a substrate comprising a polymer having the general formula PxSy, where P is a covalently crosslinked polymer and S is a supramolecular block within the polymer, wherein x+y=1 and “

y”

is greater than 0 and less than or equal to 1, wherein the supramolecular blocks are held together by noncovalent interactions between the monomer repeat units of the supramolecular block, wherein the noncovalent interactions comprise

(1) host-guest interaction between receptor-donor systems, choice of said host-guest interactions including complex of cyclodextrin with hydrophobic guest molecules, cucurbiturils with aromatic molecules, crown ethers with ionic compounds,

(2) physical crosslinking between domains formed by microphase separation, choice of said microphase separation including self-assembly of block copolymers, partial molecular fold structures, π

-π

stacking domains, and crystalline domains;

(3) noncovalent bonds between additives, choice of said additives including microparticles, nanoparticles, clay, graphene, and other inorganic additives;

(4) hydrogen bonding, choice of said hydrogen bonding including hydrogen bonds formed between urea groups;

(5) ionic bonding, choice of said ionic bonding including bonds between amino and carboxylic acid groups;

(6) coordination interaction, choice of said coordination interaction including metal-ligand coordination;

(7) entangled structures, choice of said entangled structures including entanglements formed between groups that include rotaxanes and sliding rings;

or

(8) combinations thereof;

a lubricating liquid infused within and over the polymer and

wherein the polymer and the lubricating liquid have an affinity for each other such that the infused lubricating liquid is absorbed within at least a part of the polymer to form a lubricating liquid-infused polymer while a remainder of the lubricating liquid extends from the swollen layer and forms an overlayer of the lubricating liquid, on and above a surface of the swollen layer

wherein the lubricating liquid is immiscible with the target materials and

wherein the lubricating liquid has an affinity with the polymer to maintain and replenish the overlayer by providing the lubricating liquid from said swollen layer to preserve the overlayer throughout operational life of the article.

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 further comprises silicone oil.

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

6. The article of claim 1, wherein the lubricant comprises a perfluorocarbon, a fluoroether, a fluorocarbon, a perfluorinated hydrocarbon, a fluorosilicone, a perfluoropolyether, a perfluoroalkylamine, a perfluoroalkylsulfide, a perfluoralkylsulfoxide, a perfluoroalkylether, a perfluorocycloether, a perfluoroalkylphosphine, a perfluoroalkyly phosphineoxide, a long-chain perfluorinated carboxylic acid, a fluorinated phosphonic acid, a fluorinated sulfonic acid, and/or a fluorinated silane.

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 the wt./wt. ratio of the polymer and the lubricating liquid ranges from 10:

1 to 1;

10.

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

1 to 1;

4.

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

1 to 1;

2.

12. The article of claim 1, wherein the lubricating liquid-infused polymer comprises an excess of lubricating liquid and the excess lubricating liquid is localized in lubricating liquid-rich domains within the polymer.

13. The article of claim 1, wherein the lubricating liquid is present in an amount sufficient to provide a reservoir of lubricating liquid.

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

15. The article of claim 14, 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.

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

17. The article of claim 1, wherein the target material is a biological material.

18. The article of claim 1, wherein the article comprises a roughened surface.

19. The article of claim 18, wherein the slippery lubricating layer forms a conformal layer with the roughened surface.

20. The article of claim 18, wherein the slippery lubricating layer forms flat layer over the roughened surface coating said roughened surface.

21. The article of claim 1, wherein the swollen polymer of the article contains a fluidic network and is combined with a further fluidic network adjacent to the swollen polymer such that the swollen polymer and its lubricant liquid overlayer can be infused with additional lubricating liquid to further replenish the slippery lubricating layer on the surface.

22. The article of claim 21, wherein the polymer comprising a fluidic network is a pipe or a container liner that covers the inner or outer surface of said pipe or container.

23. The article of claim 1, in which the surface comprises a coating layer on the article.

24. The article of claim 23, wherein the coating layer comprises two or more layers of liquid swollen lubricating liquid-infused polymer.

25. The article of claim 24, wherein layers of the two or more layers of lubricating liquid-infused polymer have different compositions and one of the layers is disposed on top of another to provide a complex, programmable coating.

26. The article of claim 1, wherein the article is selected from the group consisting of containers, medical devices, medical implants, gloves, membranes, filters, pipes, tubing, wires, construction materials, road signs, marine structures, and vehicles.

27. The article of claim 1, wherein the lubricating liquid further comprises a fluorinated lubricant.

28. The article of claim 1, wherein said polymer includes polyethylene glycol, silicones with vinyl groups, silanes with vinyl groups, silicones with hydrogen groups, silanes with hydrogen groups, or silicones with hydroxyl groups.

29. The article of claim 1, wherein said polymer includes polyalkyleneglycols, perfluoroalkyl groups or perfluoropolyether groups.

30. The article of claim 1, wherein said polymer includes phenyl groups or halide groups.

31. The article of claim 1, wherein said polymer includes polyethylene glycol, silicones with vinyl groups, silanes with vinyl groups, silicones with hydrogen groups, silanes with hydrogen groups, or silicones with hydroxyl groups, polyalkyleneglycols, perfluoroalkyl groups or perfluoropolyether groups, phenyl groups or halide groups.

32. The article of claim 1, wherein said polymer includes one or more polymers identified in Table 1.

33. The article of claim 1, wherein said polymer includes one or more polymers formed by the reaction of monomers, initiators and crosslinkers identified in Table 2.

34. The article of claim 1, wherein said polymer includes one or more polymers formed by the reaction of monomers, initiators and crosslinkers identified in Table 3.

35. The article of claim 1, wherein said polymer includes one or more polymers formed by the reaction of monomers, initiators and crosslinkers identified in Tables 1, 2 and 3.

36. A membrane filter that is resistant to clogging and fouling through an action of repelling fluidic target materials, the membrane comprising:

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

y”

is greater than 0 and less than or equal to 1 and having at least one pore disposed through the thickness of the membrane, each said pore open to the passage of liquid or gas there through, wherein the supramolecular blocks are held together by noncovalent interactions between the monomer repeat units of the supramolecular block, wherein the noncovalent interactions comprise

(1) host-guest interaction between receptor-donor systems, choice of said host-guest interactions including complex of cyclodextrin with hydrophobic guest molecules, cucurbiturils with aromatic molecules, crown ethers with ionic compounds,

(2) physical crosslinking between domain formed by microphase separation, choice of said microphase separation including self-assembly of block copolymers, partial molecular fold structures, π

-π

stacking domains, and crystalline domains;

(3) noncovalent bonds between additives, choice of said additives including microparticles, nanoparticles, clay, graphene, and other inorganic additives;

(4) hydrogen bonding, choice of said hydrogen bonding including hydrogen bonds formed between urea groups;

(5) ionic bonding, choice of said ionic bonding including bonds between amino and carboxylic acid groups;

(6) coordination interaction, choice of said coordination interaction including metal-ligand coordination;

(7) entangled structures, choice of said entangled structures including entanglements formed between groups that include rotaxanes and sliding rings;

or

(8) combinations thereof; 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, the polymer being of a swollen form due to the lubricating liquid within it and also having an overlayer of lubricating liquid above surfaces forming the pore of the swollen form polymer,

wherein the lubricating liquid is immiscible with the target materials and

wherein the lubricating liquid has an affinity with the polymer to maintain and replenish the overlayer by providing the lubricating liquid from said swollen layer to preserve the overlayer throughout operational life of the membrane filter.

37. The membrane filter of claim 36, 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.

38. The membrane filter of claim 36, wherein the membrane comprises a coating comprising the swellable polymer.

39. The membrane filter of claim 36, wherein the pores comprise openings/slits of the membrane filter on the order of 1 μ

m up to 1 mm in diameter.

40. The membrane of claim 36, wherein the second viscosity is greater than the first viscosity.

41. An article having a slippery surface to repel target materials, the article comprising:

a substrate comprising a polymer having the general formula PxSy, where P is a covalently cross-linked polymer and S is a supramolecular block within the polymer, wherein x+y=1 and ‘

y’

is greater than 0 and less than or equal to 1, wherein said polymer includes one or more polymers formed by the reaction of monomers, initiators and crosslinkers identified in Tables 1, 2 and 3; and

a lubricating liquid infused within and over the polymer;

wherein the polymer and the lubricating liquid have an affinity for each other such that the infused lubricating liquid is absorbed within at least a part of the polymer to form a lubricating liquid-infused polymer while a remainder of the lubricating liquid extends from the swollen layer and forms an overlayer of the lubricating liquid, on and above a surface of the swollen layer,

wherein the lubricating liquid is immiscible with the target materials, and

wherein the lubricating liquid has an affinity with the polymer to maintain and replenish the overlayer by providing the lubricating liquid from said swollen layer to preserve the overlayer throughout operational life of the article.