Graphene nanoribbon-based gas barrier composites and methods of making the same

Patent metadata

Field	Value
Publication number	US-2016237237-A1
Application number	US-201415024560-A
Country	US
Kind code	A1
Filing date	Sep 30, 2014
Priority date	Sep 30, 2013
Publication date	Aug 18, 2016
Grant date	—

Abstract

In some embodiments, the present disclosure pertains to gas barrier composites that include a polymer matrix and graphene nanoribbons dispersed in the polymer matrix. The polymer matrix can include a phase-separated block copolymer with a hard phase domain and a soft phase domain. Like-wise, the functionalized graphene nanoribbons can include edge-functionalized graphene nanoribbons with concentrations that range from about 0.1% by weight to about 5% by weight of the gas barrier composites. In some embodiments, the present disclosure pertains to methods of making gas barrier composites by dispersing graphene nanoribbons in a polymer matrix. In some embodiments, the dispersing lowers the permeability of a gas through the gas barrier composite and causes phase separation of block copolymers in the polymer matrix. In some embodiments, the dispersion of graphene nanoribbons in the polymer matrix lowers the gas effective diffusivity of the gas barrier composite by three orders of magnitude.

First claim

What is claimed is:

1 . A gas barrier composite comprising:
a polymer matrix; and graphene nanoribbons dispersed in the polymer matrix.

2 . The gas barrier composite of claim 1 , wherein the polymer matrix comprises a block copolymer.

3 . The gas barrier composite of claim 1 , wherein the polymer matrix comprises a phase-separated block copolymer.

4 . The gas barrier composite of claim 3 , wherein the phase-separated block copolymer comprises a hard phase domain and a soft phase domain.

5 . The gas barrier composite of claim 1 , wherein the polymer matrix is selected from the group consisting of styrenic block copolymers, polyolefin blends, elastomeric alloys, thermoplastic polyurethanes, poly(esters), thermoplastic co-poly(esters), thermoplastic polyamides, poly(vinyl alcohol), polyethylene terephthalate, polyethylene, polypropylene, high density polyethylene, poly(ethers), co-polymers thereof, block co-polymers thereof, and combinations thereof.

6 . The gas barrier composite of claim 1 , wherein the polymer matrix comprises thermoplastic polyurethane.

7 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise functionalized graphene nanoribbons.

8 . The gas barrier composite of claim 7 , wherein the functionalized graphene nanoribbons are selected from the group consisting of edge-functionalized graphene nanoribbons, polymer-functionalized graphene nanoribbons, alkyl-functionalization graphene nanoribbons, and combinations thereof.

9 . The gas barrier composite of claim 7 , wherein the functionalized graphene nanoribbons comprise polymer-functionalized graphene nanoribbons.

10 . The gas barrier composite of claim 9 , wherein the polymer-functionalized graphene nanoribbons are functionalized with polymers selected from the group consisting of vinyl polymers, polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, and combinations thereof.

11 . The gas barrier composite of claim 7 , wherein the functionalized graphene nanoribbons comprise alkyl-functionalized graphene nanoribbons.

12 . The gas barrier composite of claim 11 , wherein the alkyl-functionalized graphene nanoribbons are functionalized with alkyl groups selected from the group consisting of hexadecyl groups, octyl groups, butyl groups, and combinations thereof.

13 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise hexadecylated-graphene nanoribbons (HD-GNRs).

14 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons are derived from carbon nanotubes.

15 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise a single layer.

16 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise a plurality of layers.

17 . The gas barrier composite of claim 16 , wherein the graphene nanoribbons comprise from about 2 layers to about 10 layers.

18 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise from about 0.1% by weight to about 5% by weight of the gas barrier composite.

19 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons comprise about 0.5% by weight of the gas barrier composite.

20 . The gas barrier composite of claim 1 , wherein the gas barrier composite displays impermeability to a gas.

21 . The gas barrier composite of claim 20 , wherein the gas is selected from the group consisting of air, N 2 , H 2 , O 2 , CH 4 , CO 2 , natural gas, H 2 S and combinations thereof.

22 . The gas barrier composite of claim 20 , wherein the gas comprises N 2 .

23 . The gas barrier composite of claim 20 , wherein the impermeability to the gas ranges from about 50% to about 100%.

24 . The gas barrier composite of claim 20 , wherein the impermeability to the gas is more than about 50%.

25 . The gas barrier composite of claim 20 , wherein the gas barrier composite has a gas effective diffusivity (D eff ) that ranges from about 1×10 −3 m 2 /s to about 5×10 −3 m 2 /s.

26 . The gas barrier composite of claim 20 , wherein the gas barrier composite has a gas effective diffusivity (D eff ) of about 3×10 −3 m 2 /s.

27 . The gas barrier composite of claim 1 , wherein the gas barrier composite has a transparency of more than about 50%.

28 . The gas barrier composite of claim 27 , wherein the gas barrier composite has a transparency of more than about 50%, and wherein the graphene nanoribbons comprise from about 1 layer to about 4 layers.

29 . The gas barrier composite of claim 27 , wherein the gas barrier composite has a transparency of more than about 90%, and wherein the graphene nanoribbons comprise from about 1 layer to about 3 layers.

30 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons have an isotropic arrangement in the polymer matrix.

31 . The gas barrier composite of claim 1 , wherein the graphene nanoribbons have an anisotropic arrangement in the polymer matrix.

32 . The gas barrier composite of claim 1 , wherein the gas barrier composite consists essentially of graphene nanoribbons and a polymer matrix.

33 . The gas barrier composite of claim 1 , wherein the gas barrier composite lacks graphene oxide.

34 . The gas barrier composite of claim 1 , wherein the gas barrier composite lacks nanoclays.

35 . A method of making gas barrier composites, said method comprising:
dispersing graphene nanoribbons in a polymer matrix,
wherein the dispersing lowers permeability of a gas through the gas barrier composite.

36 . The method of claim 35 , wherein the dispersing occurs by a method selected from the group consisting of blending, stirring, thermal melting, layering, extrusion, sonication, solution casting, shearing, and combinations thereof

37 . The method of claim 35 , wherein the polymer matrix comprises a block copolymer, and wherein the dispersing causes phase separation of the block copolymer.

38 . The method of claim 37 , wherein the dispersing causes phase separation of the block copolymer into a soft phase domain and a hard phase domain.

39 . The method of claim 35 , wherein the polymer matrix is selected from the group consisting of styrenic block copolymers, polyolefin blends, elastomeric alloys, thermoplastic polyurethanes, poly(esters), thermoplastic co-poly(esters), thermoplastic polyamides, poly(vinyl alcohol), polyethylene terephthalate, polyethylene, polypropylene, high density polyethylene, poly(ethers), co-polymers thereof, block co-polymers thereof, and combinations thereof.

40 . The method of claim 35 , wherein the polymer matrix comprises thermoplastic polyurethane.

41 . The method of claim 35 , wherein the graphene nanoribbons comprise functionalized graphene nanoribbons.

42 . The method of claim 41 , wherein the functionalized graphene nanoribbons are selected from the group consisting of edge-functionalized graphene nanoribbons, polymer-functionalized graphene nanoribbons, alkyl-functionalization graphene nanoribbons, and combinations thereof.

43 . The method of claim 41

Assignees

• Univ Rice William M

Inventors

• Tour James M
• Xiang Changsheng

Classifications

• C08K9/04 Primary

  Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} · CPC title

• C08K2201/008

  Additives improving gas barrier properties · CPC title

• C08L75/04

  Polyurethanes · CPC title

• C08K3/04 Primary

  Carbon · CPC title

• C08K3/043

  Carbon nanocoils · CPC title