Selective interfacial mitigation of graphene defects

• US 10,213,746 B2
• Filed: 04/14/2016
• Issued: 02/26/2019
• Est. Priority Date: 04/14/2016
• Status: Active Grant

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Inventors: Liu, Han, Simon, Sarah M., Sinsabaugh, Steven Lloyd
• Primary Examiner(s): Barry, Chester T
• Application Number:
  US15/099,410
• Publication Number:
  US 20170296976A1
• Time in Patent Office: 1,048 Days
• Field of Search: None
• CPC Class Codes: B01D 2323/21 Fillers
• CPC Class Codes: B01D 2323/28 Pore treatments
• CPC Class Codes: B01D 2323/286 Closing of pores, e.g. for membrane sealing
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 2325/02831 less than 1 nm
• CPC Class Codes: B01D 2325/02832 1-10 nm
• CPC Class Codes: B01D 2325/02833 more than 10 and up to 100 nm
• CPC Class Codes: B01D 65/108 Repairing membranes
• CPC Class Codes: B01D 67/0006 by chemical reactions in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125
• CPC Class Codes: B01D 67/0023 by inducing porosity into non porous precursor membranes
• CPC Class Codes: B01D 67/0055 by mechanical treatment
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/105 Support pretreatment
• CPC Class Codes: B01D 69/1251 by interfacial polymerisation
• CPC Class Codes: B01D 71/0211 Graphene or derivates thereof

Abstract

A method for the repair of defects in a graphene or other two-dimensional material through interfacial polymerization.

Claims

1. A method comprising:

disposing a first reactant on a first side of a two-dimensional material including defects;

disposing a second reactant on a second side of the two-dimensional material such that the first reactant and second reactant undergo a polymerization reaction and form polymer regions filling the defects; and

after the polymerization reaction forms the polymer regions, adhering the polymer regions to a support structure.

2. The method of claim 1, wherein adhering the polymer regions to the support structure comprises forming covalent bonds between the polymer regions and the support structure.

3. The method of claim 1, wherein the adhering the polymer regions to the support structure comprises forming molecular entanglement between the polymer regions and the support structure.

4. The method of claim 1, further comprising adhering a polymer handling region formed along at least a portion of an edge of the two-dimensional material to the support structure.

5. The method of claim 1, wherein the two-dimensional material comprises graphene.

6. The method of claim 1, wherein the support structure is a porous support structure.

7. The method of claim 1, wherein the polymer regions have a thickness in the range of 3 nm to 100 μ

m.

8. The method of claim 1, wherein the polymer regions are biocompatible or bio-inert.

9. The method of claim 1, further comprising treating the support structure to enhance adhesion between the polymer regions and the support structure.

10. The method of claim 1, wherein the polymer regions are adhered to the support structure such that a distance between adjacent polymer regions is less than a length of the two-dimensional material between the adjacent polymer regions.

11. The method of claim 1, wherein the polymer regions are adhered to the support structure such that folds are formed in the two-dimensional material.

12. A method comprising:

forming holes in a two-dimensional material including defects;

disposing a first reactant on a first side of the two-dimensional material;

disposing a second reactant on a second side of the two-dimensional material such that the first reactant and second reactant undergo a polymerization reaction and form polymer regions filling the defects and holes; and

adhering the polymer regions to a support structure.

13. The method of claim 12, wherein the ratio of the area of the holes to the area of the two-dimensional material is in the range of 5% to 50%.

14. The method of claim 12, wherein the polymer regions have a thickness in the range of 3 nm to 100 μ

m.

15. The method of claim 12, wherein the holes are randomly distributed across the two-dimensional material.

16. The method of claim 12, wherein the holes are arranged in a periodic array.

17. The method of claim 12, wherein the polymer regions are adhered to the support structure such that a distance between adjacent polymer regions is less than a length of the two-dimensional material between the adjacent polymer regions.

18. The method of claim 12, wherein the polymer regions are adhered to the support structure such that folds are formed in the two-dimensional material.

19. A method comprising:

forming pores in a two-dimensional material including defects, wherein the defects have a size greater than 15 nm, and the pores have a size that is less than the size of the defects;

disposing a first reactant on a first side of the two-dimensional material; and

disposing a second reactant on a second side of the two-dimensional material such that the first reactant and second reactant undergo a polymerization reaction and form polymer regions filling the defects;

wherein the pores are not filled by the polymer regions.

20. The method of claim 19, wherein at least one of the first reactant and the second reactant comprises a dendrimer.

21. The method of claim 19, further comprising applying an electric potential to the two-dimensional material to attract the first reactant and the second reactant to the defects in the graphene material.

22. The method of claim 19, further comprising heating the first reactant and the second reactant to increase a rate of diffusion thereof and increase a rate of the polymerization reaction.

23. The method of claim 19, wherein the first reactant is ionic, the second reactant is ionic, and the first and second reactants have opposite charges.

24. The method of claim 19, further comprising forming holes in the two-dimensional material with a size greater than the size of the pores, such that the holes are filled by polymer regions formed during the polymerization reaction.

25. A method comprising:

disposing a first reactant on a first side of a two-dimensional material and extending beyond at least a portion of an edge of the two-dimensional material;

disposing a second reactant on a second side of the two-dimensional material and extending beyond the at least a portion of the edge of the two-dimensional material;

wherein the first reactant and second reactant undergo a polymerization reaction and form a polymer handling region at least a portion of the edge of the two-dimensional material.

26. The method of claim 25, wherein the polymer handling region extends along the entire circumference of the two-dimensional material.

27. The method of claim 25, wherein the polymer handling region extends from the at least a portion of the edge of the two-dimensional material for a distance of at least about 1 mm.

28. The method of claim 25, wherein the polymer handling region has a thickness in the range of 3 nm to 100 μ

m.

29. A method comprising:

disposing a first reactant on a first side of a two-dimensional material containing defects;

disposing a second reactant on a second side of the two-dimensional material such that the first reactant and second reactant undergo a polymerization reaction and form polymer regions filling the defects; and

forming pores in the two-dimensional material by impacting the two-dimensional material with nanoparticles.

30. The method of claim 29, wherein the nanoparticles have an energy of 2 keV to 500 keV per nanoparticle.

31. The method of claim 29, wherein the nanoparticles have a size of 2 nm to 50 nm.

32. The method of claim 29, wherein the size of the pores is from 1 nm to 100 nm.

33. The method of claim 29, wherein the fluence of the nanoparticles is 1×

10⁸ to 1×

10¹² nanoparticles/cm².

34. The method of claim 29, wherein the two-dimensional material comprises graphene.

35. A method comprising:

forming pores in a two-dimensional material including defects by impacting the two-dimensional material with nanoparticles;

disposing a first reactant on a first side of the two-dimensional material; and

disposing a second reactant on a second side of the two-dimensional material such that the first reactant and second reactant undergo a polymerization reaction and form polymer regions filling the defects;

wherein the pores are not filled by the polymer regions.

36. The method of claim 35, wherein the nanoparticles have an energy of 2 keV to 500 keV per nanoparticle.

37. The method of claim 35, wherein the nanoparticles have a size of 2 nm to 50 nm.

38. The method of claim 35, wherein the size of the pores is from 1 nm to 100 nm.

39. The method of claim 35, wherein the fluence of the nanoparticles is 1×

10⁸ to 1×

10¹² nanoparticles/cm^2.

40. The method of claim 35, wherein the two-dimensional material comprises graphene.

41. A membrane assembly, comprising:

a two-dimensional material including polymer regions that extend through defects in the two-dimensional material; and

a support structure,

wherein the two-dimensional material is adhered to the support structure via the polymer regions, and the polymer regions prevent fluid flow through the defects.

42. The membrane assembly of claim 41, wherein the two-dimensional material comprises graphene.

43. The membrane assembly of claim 41, wherein the membrane assembly is biocompatible or bio-inert.

44. The membrane assembly of claim 41, wherein the polymer regions have a thickness of 3 nm to 500 nm.

45. The membrane assembly of claim 41, wherein the polymer regions are adhered to the support structure through at least one of covalent bonds and molecular entanglement.

46. The membrane assembly of claim 41, wherein the polymer regions are adhered to the support structure such that a distance between adjacent polymer regions is less than a length of the two-dimensional material between the adjacent polymer regions.

47. The membrane assembly of claim 41, wherein the polymer regions are adhered to the support structure such that folds are formed in the two-dimensional material.