SELECTIVE MEMBRANE SUPPORTED ON NANOPOROUS GRAPHENE

• US 20150273401A1
• Filed: 11/30/2012
• Published: 10/01/2015
• Est. Priority Date: 11/30/2012
• Status: Abandoned Application

• 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.
• Application Number:
  US14/434,392
• Publication Number:
  US 20150273401A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2323/42 Details of membrane preparation apparatus
• CPC Class Codes: B01D 67/0037 by deposition from the gaseous phase, e.g. CVD, PVD
• CPC Class Codes: B01D 67/006 by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
• CPC Class Codes: B01D 67/0062 by micromachining techniques, e.g. using masking and etching steps, photolithography
• CPC Class Codes: B01D 67/0069 by deposition from the liquid phase, e.g. electrochemical deposition B01D67/0046 takes precedence
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 69/148 Organic/inorganic mixed matrix membranes
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01D 71/0211 Graphene or derivates thereof
• CPC Class Codes: B01D 71/0221 Group 4 or 5 metals
• CPC Class Codes: B01D 71/02231 Palladium
• CPC Class Codes: B01D 71/02232 Nickel
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: B01D 71/06 Organic material
• CPC Class Codes: B32B 38/0032 increasing porosity B32B38/04 takes precedence
• CPC Class Codes: Y10T 156/1056 Perforating lamina

Abstract

Technologies are generally described for composite membranes that may include a nanoporous graphene layer sandwiched between a first selective membrane and a porous support substrate. The composite membranes may be formed by depositing the selective membrane on one side of the nanoporous graphene layer, while the other side of the nanoporous graphene layer may be supported at a nonporous support substrate. The nanoporous graphene layer may be removed with the selective membrane from the nonporous support substrate and contacted to the porous support substrate to form the composite membranes. By depositing the selective membrane on a flat surface, the nanoporous graphene on the nonporous support substrate, the selective membranes may be produced with reduced defect formation at thicknesses of as little as 0.1 μm or less. The described composite membranes may have increased permeance compared to thicker selective membranes, and structural strength greater than thin selective membranes alone.

Claims

1. A composite membrane, comprising:

a nanoporous graphene layer that includes a first side and a second side, wherein the nanoporous graphene layer comprises a plurality of pores with an average diameter in a range between approximately 2 angstroms and approximately 1 micrometer;

a first selective membrane configured in contact with the first side of the nanoporous graphene layer;

a second selective membrane configured in contact with the first selective membrane, wherein at least one of the first selective membrane and the second selective membrane has an average thickness of less than approximately 1 micrometer; and

a porous support substrate configured in contact with the second side of the nanoporous graphene layer.

2. The composite membrane of claim 1, wherein the first selective membrane comprises one or more of:

a polymer, a zeolite, a metal, a metal-organic framework, or a ceramic.

3. The composite membrane of claim 2, wherein the first selective membrane 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.

4. The composite membrane of claim 1, wherein the first selective membrane has an average thickness in a range between about 10 nanometers to less than approximately 1 micrometer.

6. The composite membrane of claim 1, wherein the porous support substrate comprises a plurality of pores with an average diameter in a range between about 1 micrometer and about 1 millimeter.

5. (canceled)

7. The composite membrane of claim 1, wherein the nanoporous graphene layer includes a nanoporous graphene monolayer. 8. (canceled) 9. (canceled)

10. A method to prepare a composite membrane, comprising:

growing graphene at a nonporous growth substrate;

perforating the graphene to form a nanoporous graphene layer;

transferring the nanoporous graphene layer from the nonporous growth substrate to a nonporous support substrate;

depositing a first selective membrane at a second surface of the nanoporous graphene layer, wherein a first surface of the nanoporous graphene layer is configured in contact with the nonporous support substrate;

removing the nanoporous graphene layer together with the first selective membrane from the nonporous support substrate; and

contacting the second surface of the nanoporous graphene layer to a porous support substrate to form the composite membrane.

15. The method of claim 10, wherein the nanoporous graphene layer comprises a nanoporous graphene monolayer.

16. The method of claim 10, wherein the nanoporous graphene layer includes a plurality of pores with an average diameter in a range between about 2 angstroms and about 1 micrometer.

17. The method of claim 10, wherein depositing the first selective membrane includes depositing by one or more of:

solution deposition, electro-deposition, spin coating, dip coating, chemical growth deposition, polymerization, precipitation, chemical vapor deposition, atomic layer deposition, sputtering, or evaporative deposition.

20. The method of claim 10, wherein depositing the first selective membrane includes depositing in an average thickness in a range between about 10 nanometers and about 1 micrometer.

22. The method of claim 10, further comprising selecting the porous support substrate including a plurality of pores with an average diameter in a range between about 1 micrometer and about 1 millimeter.

23. The method of claim 10, further comprising contacting a second selective membrane to the first selective membrane, wherein at least one of the first selective membrane and the second selective membrane has an average thickness of less than about 1 micrometer.

11-14. -14. (canceled)

18-19. -19. (canceled)

21. (canceled)

24. A system to manufacture a composite membrane, the system comprising:

a chemical vapor deposition chamber;

a chemical vapor deposition source;

a heater;

a temperature sensor;

a graphene nano-perforation apparatus;

a polymer film manipulator;

a selective membrane deposition apparatus;

a porous support source; and

a controller operatively coupled to one or more of the chemical vapor deposition chamber, the chemical vapor deposition source, the heater, the temperature sensor, the graphene nano-perforation apparatus, the polymer film manipulator, the selective membrane deposition apparatus, and the porous support source, wherein the controller is configured to;

control the chemical vapor deposition source, the temperature sensor, and the heater effective to deposit graphene at a nonporous growth substrate in the chemical vapor deposition chamber;

control the graphene nano-perforation apparatus effective to perforate the graphene at the nonporous growth substrate to form a nanoporous graphene layer;

control the selective membrane deposition apparatus effective to deposit a first selective membrane on a first surface of the nanoporous graphene layer;

control the polymer film manipulator effective to remove the nanoporous graphene layer together with the first selective membrane from a nonporous support substrate;

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

control the polymer film manipulator effective to contact a second surface of the nanoporous graphene layer to a surface of the porous support substrate to form the composite membrane.

25. The system of claim 24, wherein the controller is further configured to control the polymer film manipulator effective to transfer the nanoporous graphene layer from the nonporous growth substrate to the nonporous support substrate prior to deposition of the first selective membrane on the first surface of the nanoporous graphene layer.

26. The system of claim 24, wherein the graphene nano-perforation apparatus is configured to perforate the graphene by use of one or more of:

electron beam etch, ion beam etch, atomic abstraction, colloidal lithography, block copolymer lithography, or photolithography.

27. The system of claim 24, wherein the controller is configured to control the chemical vapor deposition source, the temperature sensor, and the heater to deposit the graphene at the nonporous growth substrate as a graphene monolayer.

28. The system of claim 24, wherein the selective membrane deposition apparatus is configured to deposit the first selective membrane by one or more of:

solution deposition, electro-deposition, spin coat, dip coat, chemical growth deposition, polymerization, precipitation, chemical vapor deposition, atomic layer deposition, sputtering, or evaporative deposition.

29. The system of claim 24, wherein the selective membrane deposition apparatus is configured to deposit the first selective membrane in an average thickness in a range between about 10 nanometers and about 1 micrometer.

30. The system of claim 24, wherein the controller is further configured to control the polymer film manipulator to contact a second selective membrane to the first selective membrane.

31-34. -34. (canceled)