High flux and low fouling filtration media

• US 20100323573A1
• Filed: 10/05/2005
• Published: 12/23/2010
• Est. Priority Date: 10/06/2004
• Status: Active Grant

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: Kim, Kwang-sok, Chu, Benjamin, Fang, Dufei, Hsiao, Benjamin S.
• Granted Patent: US 8,222,166 B2
• Time in Patent Office: Days
• US Class Current: 442/153
• CPC Class Codes: B01D 2321/168 Use of other chemical agents
• CPC Class Codes: B01D 2323/38 Graft polymerization
• CPC Class Codes: B01D 2323/39 Electrospinning
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/0233 with clearly distinguishable layers
• CPC Class Codes: B01D 65/08 Prevention of membrane fouling or of concentration polarisation
• CPC Class Codes: B01D 69/107 Organic support material
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 71/08 Polysaccharides
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/259 Silicic material
• CPC Class Codes: Y10T 428/29 Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• CPC Class Codes: Y10T 428/2913 Rod, strand, filament or fiber
• CPC Class Codes: Y10T 428/2915 including textile, cloth or fabric
• CPC Class Codes: Y10T 428/2944 Free metal in coating
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 442/20 Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• CPC Class Codes: Y10T 442/2033 : Coating or impregnation formed in situ [e.g., by interfacial condensation, coagulation, precipitation, etc.]
• CPC Class Codes: Y10T 442/277 : Coated or impregnated cellulosic fiber fabric
• CPC Class Codes: Y10T 442/2861 : Coated or impregnated synthetic organic fiber fabric
• CPC Class Codes: Y10T 442/2885 : Coated or impregnated acrylic fiber fabric
• CPC Class Codes: Y10T 442/2893 : Coated or impregnated polyamide fiber fabric
• CPC Class Codes: Y10T 442/291 : Coated or impregnated polyolefin fiber fabric
• CPC Class Codes: Y10T 442/2918 : Polypropylene fiber fabric
• CPC Class Codes: Y10T 442/659 : Including an additional nonwoven fabric

Abstract

Membranes suitable for microfiltration, ultrafiltration (UF) and nanofiltration (NF) filters are provided. Such membranes may include a nanofibrous scaffold, optionally in combination with a non-woven substrate and/or a coating of a polymer and a functionalized nanofiller. Suitable membranes may also include a coating of a polymer and a functionalized nanofiller on a substrate, which can include a non-woven membrane, a nanofibrous scaffold, or both.

Claims

1. An article comprising:

a substrate; and

a coating on said substrate comprising a polymer in combination with at least one nanofiller having a diameter from about 0.3 nm to about 300 nm.

2. The article of claim 1 wherein the polymer is a hydrophilic polymer selected from the group consisting of polysaccharides, polyalcohols, polyalkylene oxides, polyimines, polyacrylic acids, polyamides, polyamines, polyurethanes, polyureas, derivatives thereof and copolymers thereof.

3. The article of claim 1 wherein the polymer is a hydrophilic polymer selected from the group consisting of chitosan, cellulose, cellulose acetate, collagen, gelatin, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyethylene glycol-grafted chitosan, polyethylene glycol-grafted polymethyl methacrylate, polyethylene imine, polyvinylpyrrolidone, poly(ether-co-amide) copolymers, polybenzimidazole, nylon 6, nylon 66, nylon 12, polyallylamine, derivatives thereof and copolymers thereof.

4. The article of claim 1 wherein the polymer is a hydrophobic polymer selected from the group consisting of polyolefins, polysulfones, fluoropolymers, polyesters, polycarbonates, polystyrenes, polynitriles, polyacrylates, polyacetates, derivatives thereof and copolymers thereof.

5. The article of claim 4 wherein the polymer is a hydrophobic polymer selected from the group consisting of polyethylene, polypropylene, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polystyrene, polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, derivatives thereof and copolymers thereof.

6. The article of claim 1, wherein the coating layer has a thickness of from about 1 nm to about 4000 nm.

7. The article of claim 1 wherein the nanofiller has a length of from about 1 nm to about 500 microns.

8. The article of claim 1 wherein the nanofiller is selected from the group consisting of organic nanofillers and inorganic nanofillers.

9. The article of claim 1 wherein the nanofiller is selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, bucky balls, functionalized graphite nanoparticles, functionalized gold nanoparticles, functionalized cobalt nanoparticles, functionalized cadmium nanoparticles, functionalized copper nanoparticles, functionalized iron nanoparticles, functionalized lead nanoparticles, functionalized zinc nanoparticles, functionalized palladium nanoparticles, silica, polyhedral oligomeric silsesquioxanes, layered silicates, functionalized inorganic nanotubes containing metallic compounds selected from the group consisting of gold, cobalt, cadmium, copper, iron, lead, zinc and palladium, and derivatives thereof.

10. The article of claim 1 wherein the nanofiller is functionalized with a monomer or oligomer of the polymer comprising the coating.

11. The article of claim 1 wherein the nanofiller comprises carbon nanotubes selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanofibers having a diameter of from about 1 nm to about 100 nm, optionally functionalized with a monomer or oligomer of the polymer comprising the coating.

12. The article of claim 1, wherein the coating has, a pore or channel size of from about 0.2 nm to about 30 nm.

13. The article of claim 1, wherein the nanofiller is present in the coating in an amount of from about 0.1 percent by weight to about 95 percent by weight of the coating.

14. The article of claim 1, wherein the coating comprises from about 1 to about 5 different nanofillers.

15. The article of claim 1, wherein the nanofiller is functionalized with at least one hydrophilic functional group selected from the group consisting of carboxylic acid groups, carbonyl groups, hydroxy groups, ethylene oxides, alcohols, saccharides, amine groups, DNA, and protein fragments.

16. The article of claim 1, wherein the nanofiller is functionalized with at least one hydrophobic group selected from the group consisting of linear aliphatic compounds having from about 1 to about 20 carbon atoms, and aromatic hydrocarbons.

17. The article of claim 1, wherein the substrate is a nonwoven polymer selected from the group consisting of polyolefins, polyesters, polyamides, polyurethanes, fluorinated polymers, derivatives thereof and copolymers thereof.

18. The article of claim 1 wherein the substrate is a nonwoven polymer selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, nylon 12, derivatives thereof and copolymers thereof.

19. The article of claim 1, wherein the substrate comprises a nanofibrous scaffold comprising fibers having a diameter of from about 1 nm to about 20,000 nm.

20. The article of claim 19 wherein the nanofibrous scaffold comprises a polymer selected from the group consisting of polyolefins, polysulfones, fluoropolymers, polyesters, polyamides, polycarbonates, polystyrenes, polynitriles, polyacrylates, polyacetates polyalcohols, polysaccharides, polyalkylene oxides, polyurethanes, polyureas, polyimines polyacrylic acids, polysiloxanes, poly(ester-co-glycol) copolymers, poly(ether-co-amide) copolymers, derivatives thereof and copolymers thereof.

21. The article of claim 19 wherein the nanofibrous scaffold comprises a polymer selected from the group consisting of polyethylene, polypropylene, polyethersulfone, polyvinylidene fluoride, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, nylon 12, polystyrene, polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, chitosan, cellulose, collagen, gelatin, polyethylene oxide, polyethylene glycol, polyvinyl chloride, polyethylene imine, polyvinylpyrrolidone, polydimethylsiloxane, derivatives thereof and copolymers thereof.

22. The article of claim 19 wherein the nanofibrous scaffold further comprises at least one nanofiller having a diameter from about 0.3 nm to about 300 nm.

23. The article Of claim 13 wherein the nanofibrous scaffold has a thickness of from about 1 μ

m to about 500 μ

m.

24. The article of claim 19, wherein the nanofibrous scaffold possesses voids with an effective diameter of from about 2 nm to about 200 μ

m.

25. An article comprising a nanofibrous scaffold comprising:

fibers having a diameter of from about 1 nm to about 20,000 nm;

voids with an effective diameter of from about 2 nm to about 200 μ

m; and

a thickness of from about 1 μ

m to about 500 μ

m.

26. The article of claim 25 wherein the nanofibrous scaffold comprises a polymer selected from the group consisting of polyolefins, polysulfones, fluoropolymers, polyesters, polyamides, polycarbonates, polystyrenes, polynitriles, polyacrylates, polyacetates polyalcohols, polysaccharides, polyalkylene oxides, polyurethanes, polyureas, polyimines polyacrylic acids, polysiloxanes, poly(ester-co-glycol) copolymers, poly(ether-co-amide) copolymers, derivatives thereof and copolymers thereof.

27. The article of claim 25 wherein the nanofibrous scaffold comprises a polymer selected from the group consisting of polyethylene, polypropylene, polyethersulfone, polyvinylidene fluoride, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, nylon 12, polystyrene, polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, chitosan, cellulose, collagen, gelatin, polyethylene oxide, polyethylene glycol, polyvinyl chloride, polyethylene imine, polyvinylpyrrolidone, polydimethylsiloxane, derivatives thereof and copolymers thereof.

28. The article of claim 25 wherein the nanofibrous scaffold comprises at least one layer prepared from at least one solution of at least one polymer utilizing a process selected from the group consisting of electro-spinning, electro-blowing, blowing-assisted electro-spinning, and solution blowing.

29. The article of claim 28 wherein the nanofibrous scaffold comprises from about 1 to about 5 layers prepared from about 1 to about 5 solutions of from about 1 to about 5 polymers.

30. The article of claim 28 wherein the polymer is in a solvent selected from the group consisting of N,N-dimethyl formamide, tetrahydrofuran, methylene chloride, dioxane, ethanol, propanol, butanol, chloroform, water, and mixtures thereof.

31. The article of claim 30 wherein the polymer is present in the solvent at an amount ranging from about 1 to about 50 percent by weight.

32. The article of claim 28 wherein the nanofibrous scaffold is electrospun using a field strength from about 0.5 to about 5 kV/cm with a solution flow rate of from about 5 to about 100 μ

l/min.

33. The article of claim 25, further comprising a substrate comprising a nonwoven polymer selected from the group consisting of polyolefins, polyesters, polyamides, polyurethanes, fluorinated polymers, derivatives thereof and copolymers thereof.

34. The article of claim 33 wherein the substrate comprises a polymer selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, nylon 12, derivatives thereof and copolymers thereof.

35. The article of claim 33 further comprising an adhesive layer between the substrate and the nanofibrous scaffold.

36. The article of claim 35 wherein the adhesive layer is selected from the group consisting of chitosan, collagen, gelatin, polyvinyl alcohol, polyethylene oxide, derivatives thereof, and copolymers thereof.

37. The article of claim 25 further comprising a coating on the nanofibrous scaffold of a polymer in combination with at least one nanofiller having a diameter ranging from about 0.3 nm to about 300 nm.

38. The article of claim 25 wherein the nanofibrous scaffold further comprises at least one nanofiller having a diameter from about 0.3 nm to about 300 nm.

39. An article comprising

a substrate;

a nanofibrous scaffold comprising fibers having a diameter of from about 1 nm to about 20,000 nm applied to a surface of the substrate; and

a coating on said nanofibrous scaffold on a surface opposite a surface applied to said substrate comprising a polymer in combination with at least one functionalized nanofiller having a diameter ranging from about 1 nm to about 100 nm.

40. An article comprising an asymmetric nanofibrous scaffold layer having a bottom surface and a top surface, the fibers making up the bottom surface of the nanofibrous scaffold having a diameter from about 300 nm to about 10,000 nm, and the fibers making up the top surface of the nanofibrous scaffold having a diameter from about 10 nm to about 500 nm, wherein the diameter of the fibers making up the bottom surface of the nanofibrous scaffold is greater than the diameter of the fibers making up the top surface of the nanofibrous scaffold.