GRAPHENE MEMBRANE LAMINATED TO POROUS WOVEN OR NONWOVEN SUPPORT

• US 20140151288A1
• Filed: 11/30/2012
• Published: 06/05/2014
• Est. Priority Date: 11/30/2012
• Status: Active Grant

• Current Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Original Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Inventors: Miller, Seth Adrian, Duerksen, Gary L.
• Granted Patent: US 9,656,214 B2
• Time in Patent Office: Days
• US Class Current: 210/497.01
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 69/1213 Laminated layers
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B01D 71/0211 Graphene or derivates thereof
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 15/14 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 2262/0253 Polyolefin fibres
• CPC Class Codes: B32B 2262/106 Carbon fibres, e.g. graphite fibres
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 27/28 comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B32B 27/38 comprising epoxy resins
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: B32B 3/266 characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
• CPC Class Codes: B32B 5/022 Non-woven fabric
• CPC Class Codes: B32B 5/024 Woven fabric
• CPC Class Codes: B32B 9/007 comprising carbon, e.g. graphite, composite carbon
• CPC Class Codes: B32B 9/041 : of metal

Abstract

Technologies are generally described for composite membranes which may include a porous graphene layer in contact with a porous support substrate. In various examples, a surface of the porous support substrate may include at least one of: a thermo-formed polymer characterized by a glass transition temperature, a woven fibrous membrane, and/or a nonwoven fibrous membrane. Examples of the composite membranes permit the use of highly porous woven or nonwoven fibrous support membranes instead of intermediate porous membrane supports. In several examples, the composite membranes may include porous graphene layers directly laminated onto the fibrous membranes via the thermo-formed polymers. The described composite membranes may be useful for separations, for example, of gases, liquids and solutions.

Claims

1. A composite membrane, comprising:

a porous graphene layer; and

a porous support substrate that includes a surface configured in contact with the porous graphene layer,

wherein the surface of the porous support substrate includes at least one of;

a thermo-formed polymer characterized by a glass transition temperature, a woven fibrous membrane, and/or a nonwoven fibrous membrane, wherein at least one additional woven fibrous membrane or nonwoven fibrous membrane is configured in contact with the porous support substrate, and wherein the porous support substrate is substantially fibrous.

2. The composite membrane of claim 1, wherein the surface of the porous support substrate comprises one or more of:

an acrylonitrile-butadiene-styrene, an allyl resin, a carbon fiber, a cellulosic resin, an epoxy, a polyalkylene vinyl alcohol, a fluoropolymer, a melamine formaldehyde resin, a phenol-formaldehyde resin, a polyacetal, a polyacrylate, a polyacrylonitrile, a polyacrylonitrile, a polyalkylene, a polyalkylene carbamate, a polyalkylene oxide, a polyalkylene sulphide, a polyalkylene terephthalate, a polyalkyl alkylacrylate, a polyalkyleneamide, a halopolyalkylene, a polyamide, a polyamide-imide, a polyarylene isophthalamide, a polyarylene oxide, a polyarylene sulfide, a polyaramide, a polyarylene terephthalamide, a polyaryletherketone, a polycarbonate, a polybutadiene, a polyketone, a polyester, a polyetheretherketone, a polyetherimide, a polyethersulfone, a polyimide, a polyphthalamide, a polystyrene, a polysulfone, a polytetrafluoroalkylene, a polyurethane, a polyvinyl alkyl ether, a polyvinylhalide, a polyvinylidene halide, a silicone polymer, or a combination or a copolymer thereof.

3. The composite membrane of claim 1, wherein the thermo-formed polymer includes a distribution of pores characterized by an average pore diameter in a range between about 5 nanometers and about 25 micrometers.

4. The composite membrane of claim 1, wherein the thermo-formed polymer corresponds to the woven fibrous membrane or the nonwoven fibrous membrane.

5. The composite membrane of claim 1, wherein the woven fibrous membrane or the nonwoven fibrous membrane includes a distribution of pores characterized by an average pore diameter in a range between about 5 nanometers and about 250 micrometers.

6. The composite membrane of claim 5, wherein the distribution of pores is characterized in that less than about one pore per billion in the distribution of pores has a diameter greater than about 4 times the average pore diameter.

7. The composite membrane of claim 5, wherein the woven fibrous membrane or the nonwoven fibrous membrane is substantially comprised of fibers in a range from about 0.1 denier to about 3 denier.

10. The composite membrane of claim 1, further comprising a porous metal support configured in contact with at least one of the porous support substrate and the porous graphene layer, wherein a porous metal substrate includes one or more of:

a metal mesh, a metal screen, a metal grid, a perforated metal layer, or a spiral bound mesh.

8-9. -9. (canceled)

11. A method of preparing a composite membrane, comprising:

contacting a second surface of a porous graphene layer to a first surface of an adherent polymer or a thermo-formable polymer, wherein a first surface of the porous graphene layer is configured in contact with a growth substrate;

removing the porous graphene layer together with the adherent polymer from the growth substrate to form the composite membrane or heating the first surface of the porous graphene layer and the thermo-formable polymer above a glass transition temperature;

contacting the first surface or the second surface of the porous graphene layer to a surface of a porous support substrate to form the composite membrane,

wherein the surface of the porous support substrate includes at least one of;

the first surface of the adherent polymer, a thermo-formable polymer characterized by a glass transition temperature, a woven fibrous membrane, and/or a nonwoven fibrous membrane; and

heating the porous graphene layer and the adherent polymer above the glass transition temperature while contacting the second surface of the porous graphene layer to the first surface of the adherent polymer.

12. The method of claim 11, further comprising:

contacting the surface of the porous support substrate to the first surface of the porous graphene layer or a second surface of the adherent polymer; and

removing the adherent polymer from the porous graphene layer to form the composite membrane.

15. The method of claim 11, further comprising forming the first surface of the adherent polymer by coating the adherent polymer onto the woven fibrous membrane or the nonwoven fibrous membrane.

16. The method of claim 11, further comprising heating the porous graphene layer and the adherent polymer above the glass transition temperature while contacting the second surface of the porous graphene layer to the first surface of the adherent polymer, wherein the adherent polymer corresponds to the woven fibrous membrane or the nonwoven fibrous membrane.

17. The method of claim 11, further comprising selecting the surface of the porous support substrate including one or more of:

an acrylonitrile-butadiene-styrene, an allyl resin, a carbon fiber, a cellulosic resin, an epoxy, a polyalkylene vinyl alcohol, a fluoropolymer, a melamine formaldehyde resin, a phenol-formaldehyde resin, a polyacetal, a polyacrylate, a polyacrylonitrile, a polyacrylonitrile, a polyalkylene, a polyalkylene carbamate, a polyalkylene oxide, a polyalkylene sulphide, a polyalkylene terephthalate, a polyalkyl alkylacrylate, a polyalkyleneamide, a halopolyalkylene, a polyamide, a polyamide-imide, a polyarylene isophthalamide, a polyarylene oxide, a polyarylene sulfide, a polyaramide, a polyarylene terephthalamide, a polyaryletherketone, a polycarbonate, a polybutadiene, a polyketone, a polyester, a polyetheretherketone, a polyetherimide, a polyethersulfone, a polyimide, a polyphthalamide, a polystyrene, a polysulfone, a polytetrafluoroalkylene, a polyurethane, a polyvinyl alkyl ether, a polyvinylhalide, a polyvinylidene halide, a silicone polymer, or a combination or a copolymer thereof.

19. The method of claim 11, further comprising selecting the woven fibrous membrane or the nonwoven fibrous membrane including a distribution of pores characterized by an average pore diameter in a range between about 5 nanometers and about 250 micrometers.

20. The method of claim 11, further comprising selecting the woven fibrous membrane or the nonwoven fibrous membrane including a distribution of pores characterized in that less than about one pore per billion in the distribution of pores has a diameter greater than 4 times an average pore diameter.

21. The method of claim 11, further comprising selecting the woven fibrous membrane or the nonwoven fibrous membrane substantially comprising fibers in a range between about 0.1 denier to about 3 denier.

22. The method of claim 11, further comprising contacting the porous support to at least one additional woven fibrous membrane or nonwoven fibrous membrane, wherein the surface of the porous support substrate includes the woven fibrous membrane or the nonwoven fibrous membrane.

23. The method of claim 11, further comprising contacting the porous support substrate and/or the porous graphene to a porous metal support, wherein the porous metal substrate includes one or more of:

a metal mesh, a metal screen, a metal grid, a perforated metal layer, or a spiral bound mesh.

13. (canceled)

14. (canceled)

18. (canceled)

24. A system for manufacturing a composite membrane, the system comprising:

an adherent polymer source;

a polymer film manipulator;

a sample manipulator

a heater;

a temperature sensor;

a porous support source; and

a controller coupled to one or more of the adherent polymer source, the polymer film manipulator, and the porous support source, wherein the controller is configured by machine-executable instructions to;

control the adherent polymer source and the sample manipulator effective to contact a first surface of an adherent polymer to a second surface of a porous graphene layer, the porous graphene layer having a first surface that contacts a growth substrate;

control the porous support source effective to provide a porous support substrate;

control the polymer film manipulator effective to contact the surface of the porous support substrate to the first surface of the porous graphene layer or the second surface of the adherent polymer, remove the porous graphene layer together with the adherent polymer from the growth substrate, and remove the adherent polymer from the porous graphene layer to form the composite membrane;

control the porous support source effective to provide a porous support substrate;

control the polymer film manipulator effective to contact the first surface or the second surface of the porous graphene layer to a surface of the porous support substrate to form the composite membrane, wherein the surface of the porous support substrate includes at least one of;

the first surface of the adherent polymer, a thermo-formable polymer characterized by a glass transition temperature, a woven fibrous membrane, or a nonwoven fibrous membrane; and

control the heater and the temperature sensor to heat one of the adherent polymer, the thermo-formable polymer, the woven fibrous membrane, or the nonwoven fibrous membrane over a glass transition temperature;

control the sample manipulator and the polymer film manipulator to;

contact the surface of the porous support substrate to the first surface of the porous graphene layer or the second surface of the adherent polymer;

remove the adherent polymer from the porous graphene layer to form the composite membrane; and

contact the adherent polymer onto the woven fibrous membrane or the nonwoven fibrous membrane.

27. The system of claim 24, further comprising a sample manipulator operatively coupled to the controller, wherein the controller is further configured by the machine-executable instructions to control the heater, the temperature sensor, the sample manipulator, and the polymer film manipulator effective to:

contact the surface of the porous support substrate to the first surface of the porous graphene layer, wherein the surface of the porous substrate includes the thermo-formable polymer; and

heat the first surface of the porous graphene layer and the thermo-formable polymer above the glass transition temperature.

28. The system of claim 24, further comprising a sample manipulator operatively coupled to the controller, wherein the controller is further configured by the machine-executable instructions to control the heater, the temperature sensor, the sample manipulator, and the polymer film manipulator effective to:

heat the porous graphene layer and the adherent polymer above the glass transition temperature; and

contact the second surface of the porous graphene layer to the first surface of the adherent polymer, wherein the adherent polymer corresponds to the thermo-formable polymer.

29. The system of claim 24, further comprising a sample manipulator operatively coupled to the controller, wherein the controller is further configured by the machine-executable instructions to control the sample manipulator, the polymer film manipulator, and the adherent polymer source effective to contact the adherent polymer onto the woven fibrous membrane or the nonwoven fibrous membrane.

30. The system of claim 24, further comprising a sample manipulator operatively coupled to the controller, wherein the controller is further configured by the machine-executable instructions to control the heater, the temperature sensor, the sample manipulator, and the polymer film manipulator effective to:

heat the porous graphene layer and the adherent polymer above the glass transition temperature; and

contact the second surface of the porous graphene layer to the first surface of the adherent polymer, wherein the adherent polymer is the woven fibrous membrane or the nonwoven fibrous membrane.

25. (canceled)

26. (canceled)

31-35. -35. (canceled)