Modification of surfaces for fluid and solid repellency

Patent metadata

Field	Value
Publication number	US-2016144079-A1
Application number	US-201414904399-A
Country	US
Kind code	A1
Filing date	Jul 10, 2014
Priority date	Jul 10, 2013
Publication date	May 26, 2016
Grant date	—

Abstract

Articles, methods of making, and uses for modifying surfaces for liquid repellency are disclosed. The liquid repellant surfaces comprise a surface comprising an anchoring layer. The anchoring layer, which forms an immobilized molecular anchoring layer on the surface, has anchoring molecules, where each anchoring molecule has a head group that is covalently linked to the surface and a functional tail group. The anchoring molecules are crosslinked to each other to form a crosslinked network. The functional tail group has an affinity for a lubricating liquid, which is applied to the treated surface to form a lubricating layer. The anchoring layer and replenishable lubricating liquid are held together by non-covalent attractive forces. Together, these layers form an ultra-repellant slippery surface that repels certain immiscible liquids and prevents adsorption, coagulation, and surface fouling by components contained within.

First claim

1 . An article having a slippery surface, comprising:
a substrate comprising an anchoring layer, the anchoring layer comprising;
anchoring molecules comprising a head group attached to the substrate and a functional tail group directly or indirectly attached to the head group; and
a crosslinking agent that crosslinks the anchoring molecules to one another
a lubricating layer comprising a lubricating liquid having an affinity for the functional tail group and disposed over the anchoring layer, wherein the anchoring layer and the lubricating layer are held together by non-covalent attractive forces,
wherein the anchoring layer and the lubricating layer form a slippery surface configured and arranged for contact with a material that is substantially immiscible with the lubricating liquid,
wherein the article is substantially free of anchoring molecules not bound to the substrate, unreacted crosslinking agent, and reaction byproducts between the anchoring molecules and the crosslinking agent.

2 . The article of claim 1 , wherein the immiscible material is selected from the group consisting of a liquid, complex fluid, solution, suspension, a gas and a solid.

3 . The article of claim 1 , wherein the slippery surface is hydrophobic.

4 . The article of claim 1 , wherein the slippery surface is hydrophilic.

5 . The article of claim 1 , wherein the slippery surface is omniphobic.

6 . The article of claim 1 , wherein said head group of the anchoring molecules include ethers, silyl ethers, siloxanes, esters of carboxylic acids, esters of sulfonic acids, esters of sulfinic acids, esters of sulfuric acids, esters of phosphonic acids, esters of phosphinic acids, esters of phosphoric acids, silyl esters of carboxylic acids, silyl esters of sulfonic acids, silyl esters of sulfinic acids, silyl esters of sulfuric acids, silyl esters of phosphonic acids, silyl esters of phosphinic acids, silyl esters of phosphoric acids, oxides, sulfides, carbocycles, heterocycles with at least one oxygen atom, heterocycles with at least one nitrogen atom, heterocycles with at least one sulfur atom, heterocycles with at least one silicon atom, ‘click’ reactions-derived heterocycles, Diels-Alder reactions-derived carbocycles, Diels-Alder reactions-derived heterocycles, amides, imides, sulfides, thiolates, metal thiolates, urethanes, oximes, hydrazides, hydrazones, physisorbed or chemisorbed or otherwise non-covalently attached moieties, or combinations thereof.

7 . The article of claim 1 , wherein the functional tail group of the anchoring molecules comprise a hydrocarbon, and the lubricating layer comprises hydrocarbon liquid, wherein the anchoring layer and the lubricating layer form an hydrophobic slippery surface.

8 . The article of claim 7 , wherein said functional tail group of the anchoring molecules include alkanes, alkenes, alkynes, and aromatic compounds, and combinations thereof.

9 . The article of claim 1 , wherein the functional tail group of the anchoring molecules comprise charged polypeptides, polyanions, polycations, polar polymers, polysaccharides, amines, carboxylic acids, guanidine, alcohols, sulfhydryls, carboxamides, metal oxides, or combinations thereof.

10 . The article of claim 1 , wherein the functional tail group of the anchoring molecules includes perfluorocarbons, perfluorooligoethers and perfluoropolyethers.

11 . The article of claim 1 , wherein, the anchoring molecules comprise a silyl group covalently attached to a hydrocarbon or perfluorocarbon tail, and the lubricating layer comprises hydrocarbon or perfluorocarbon liquid, wherein the anchoring layer and the lubricating layer form a hydrophobic or an omniphobic slippery surface.

12 . The article of claim 1 , wherein, the anchoring molecules comprise a phosphonate or carboxylate group covalently attached to a hydrocarbon or perfluorocarbon tail, and the lubricating layer comprises hydrocarbon or perfluorocarbon liquid, wherein the anchoring layer and the lubricating layer form a hydrophobic or an omniphobic slippery surface.

13 . The article of claim 1 , wherein the slippery surface is slippery to water-based and hydrocarbon-based liquids.

14 . The article of claim 1 , wherein the slippery surface is slippery to biological fluids.

15 . The article of claim 1 , wherein the slippery surface is slippery to non-heparinized blood.

16 . The article of claim 1 , wherein the slippery surface comprises beads, hollow fibers, membranes, thin films, tubing, fluidized bed, filters, mixers, impellers, connectors, cannula, flow cells, or needles.

17 . The article of claim 1 , wherein the surface comprises medical grade materials or medical devices.

18 . A method of preventing adhesion, adsorption, surface-mediated clot formation, or coagulation of a material onto a substrate, comprising
providing a slippery surface comprising an anchoring layer, the anchoring layer comprising anchoring molecules having a head group attached to a substrate and a functional tail group directly or indirectly attached to the head group and crosslinking agents that crosslink the anchoring molecules to one another; and a lubricating layer comprising a lubricating liquid having an affinity for the functional tail group and disposed over the anchoring layer, wherein the slippery surface is substantially free of anchoring molecules not bound to the substrate, unreacted crosslinking agent, and reaction byproducts between the anchoring molecules and the crosslinking agent, and wherein the anchoring layer and the lubricating layer are held together by non-covalent attractive forces; and contacting an immiscible material to the slippery surface.

19 . The method of claim 18 , wherein the head group is covalently attached to the surface.

20 . The method of claim 18 , wherein the anchoring layer forms a monomolecular layer on the surface.

21 . The method of claim 18 , wherein the surface is selected from the group consisting of acrylic, glass, polymers, metals, carbon, plastics, paper, ceramics, and combinations thereof.

22 . The method of claim 18 , wherein the surface is treated to activate the surface prior to exposure to the anchoring layer.

23 . The method of claim 22 , wherein activation comprises acid treatment, base treatment, oxidization, ammonization, heat, peroxide, photon, electron, ion, plasma, or microwave treatment.

24 . The method of claim 18 , wherein the slippery surface is hydrophobic.

25 . The method of claim 18 , wherein the slippery surface is hydrophilic.

26 . The method of claim 18 , wherein the slippery surface is omniphobic.

27 . The method of claim 18 , wherein the functional tail group is a hydrocarbon.

28 . The method of claim 18 , wherein the functional tail group is selected from the group consisting of charged polypeptides, polyanions, polycations, polar polymers, polysaccharides, amines, carboxylic acids, guanidine, alcohols, sulfhydryls, carboxamides, metal oxides and combinations thereof.

29 . The method of claim 18 , wherein the functional tail group is a fluorocarbon.

30 . The method of claim 18 , wherein the immiscible material is selected from the group consisting of non-viscous and viscous liquids, complex fluids, semi-solids, tacky liquids, solids and combinations thereof.

31 . The method of claim 18 , wherein the

Assignees

• Harvard College

Inventors

• Ingber Donald
• Leslie Daniel C
• Super Michael
• Watters Alexander L
• Waterhouse Anna

Classifications

• A61L29/08

  Materials for coatings · CPC title

• C09D5/16

  Antifouling paints; Underwater paints · CPC title

• A61L31/08 Primary

  Materials for coatings · CPC title

• A61L2400/10

  Materials for lubricating medical devices · CPC title

• A61L2420/02

  Methods for coating medical devices · CPC title