Electrically conductive polymer compositions containing metal particles and a graphene and methods for production and use thereof

• US 8,167,190 B1
• Filed: 05/06/2011
• Issued: 05/01/2012
• Est. Priority Date: 05/06/2011
• Status: Expired due to Fees

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Inventors: Vanderwiel, Robert W., Bullock, Steven
• Primary Examiner(s): STONER, KILEY SHAWN
• Application Number:
  US13/103,016
• Time in Patent Office: 361 Days
• Field of Search: None
• US Class Current: 228/119
• CPC Class Codes: B23K 1/0008 specially adapted for particular articles or work
• CPC Class Codes: B23K 1/0016 Brazing of electronic components
• CPC Class Codes: B23K 1/018 Unsoldering; Removal of melted solder or other residues
• CPC Class Codes: B23K 2101/006 Vehicles
• CPC Class Codes: B23K 2101/40 Semiconductor devices
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon

Abstract

Polymer compositions containing a polymer matrix, a graphene that is covalently bonded to the polymer matrix and metal particles are described herein. A combined concentration of the metal particles and the graphene in the polymer matrix exceeds an electrical percolation threshold. In general, the graphene has a carbon:oxygen ratio of at least about 20:1 so as to impart a high electrical conductivity thereto. The polymer compositions can be used as a lead-free solder material, in which case they can allow multiple rework operations to take place at a connection. Methods for making and using such electrically conductive polymer compositions are also described.

Claims

1. A polymer composition comprising:

a polymer matrix;

a graphene that is covalently bonded to the polymer matrix; and

metal particles having an additive covalently bonded thereto;

wherein the additive comprises a thiol, a silane, a silanol, a monodentate amine, a bidentate amine, or any combination thereof; and

wherein a combined concentration of the metal particles and the graphene in the polymer matrix exceeds an electrical percolation threshold.

2. The polymer composition of claim 1, wherein the polymer composition comprises a lead-free solder material.

3. The polymer composition of claim 1, wherein the polymer matrix comprises a thermoplastic material.

4. The polymer composition of claim 3, wherein the thermoplastic material comprises polar functional groups that are reactive with the graphene.

5. The polymer composition of claim 3, wherein the thermoplastic material comprises a polymer selected from the group consisting of polyacrylic acid, polyacrylates, polymethacrylic acid, polymethacrylates, polyvinyl alcohol, polyvinyl acetate, polycarbonates, acrylic acid copolymers, acrylate copolymers, methacrylic acid copolymers, methacrylate copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, styrene copolymers, derivatives thereof, and combinations thereof.

6. The polymer composition of claim 1, wherein the graphene has a carbon:

oxygen ratio of at least about 20;

1.

7. The polymer composition of claim 1, wherein the graphene has a carbon:

oxygen ratio of at least about 100;

1.

8. The polymer composition of claim 1, further comprising:

at least one antioxidant material.

9. The polymer composition of claim 1, wherein the metal particles comprise metal nanoparticles that are at most about 100 nm in size.

10. The polymer composition of claim 1, wherein the metal particles comprise metal nanoparticles that are at most about 20 nm in size.

11. The polymer composition of claim 1, wherein the additive further comprises a functional group that is reactive with the polymer matrix, the graphene, or both.

12. The polymer composition of claim 11, wherein at least a portion of the metal particles are covalently bonded to the polymer matrix, the graphene, or both.

13. The polymer composition of claim 1, wherein the additive is selected from the group consisting of 1,3,4-thiadiazole, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 1,2,4-triazole-3-thiol, 1-pyrollidinecarbodithioic acid, 2,2′

-dithiobis(benzothiazole), 2,4-dimercapto-6-amino-5-triazine, 2,4-dithiohydantoin, 2,5-dimethylbenzothiazole, 2-amino-1,3,4-thiadiazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidizole, 2-mercaptobenzoxazole, 2-mercaptoethane sulfonic acid, 2-mercaptoimidazole, 2-mercaptothiazoline, 2-thiouracil, 3-amino-5-mercapto-1,2,4-triazole, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, 5-amino-1,3,4-thiadiazole, 6-amino-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-mercaptopurine, N-cycloalkyl-dithiocarbamates, alkyl- and cycloalkyl mercaptans, benzothiazoles, dimercaptopyridines, dimethyldithiocarbamic acid, dithiocyanuric acid, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptoethanesulfonic acid, mercaptoimidazoles, mercaptopyridines, mercaptopyrimidines, mercaptoquinolines, mercaptothiazoles, mercaptothiazolines, mercaptotriazoles, O,O-dialkyl- and O,O-dicycloalkyldithiophosphates, O-alkyl- or O-cycloalkyldithiocarbonates, o-ethylxanthic acid, quinoxaline-2,3-thiol, thioacetic acid, thiocresol, thiosalicylic acid, trithiocyanuric acid, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzothiazole, diethyldithiocarbamic acid, 5-amino-1,3,4,-thiadiazole-2-thiol, 1,2,3-benzothiazole, 1-pyrollidinecarbodithioic acid, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methylbenzimidazole, mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, trithiocyanuric acid, 2,4-dithiohydantoin, 2,4-dimercapto-6-amino-5-triazine, silanes, silanols, derivatives thereof, and mixtures thereof.

14. The polymer composition of claim 1, wherein the metal particles comprise at least one metal selected from the group consisting of copper, tin, aluminum, silver and gold.

15. The polymer composition of claim 1, wherein the polymer composition has a sheet resistivity of less than about 0.01 ohm/square.

16. A polymer composition comprising:

a polymer matrix comprising a thermoplastic material;

a graphene that is covalently bonded to the thermoplastic material;

wherein

     1) the graphene has a carbon;

oxygen ratio of at least about 20;

1; and

metal particles having an additive covalently bonded thereto;

2) the additive comprises a thiol, a silane, a silanol, a monodentate amine, a bidentate amine, or any combination thereof and

     3) a combined concentration of the metal particles and the graphene in the polymer matrix exceeds an electrical percolation threshold.

17. The polymer composition of claim 16, wherein the thermoplastic material comprises a polymer selected from the group consisting of polyacrylic acid, polyacrylates, polymethacrylic acid, polymethacrylates, polyvinyl alcohol, polyvinyl acetate, polycarbonates, acrylic acid copolymers, acrylate copolymers, methacrylic acid copolymers, methacrylate copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, styrene copolymers, derivatives thereof, and combinations thereof.

18. The polymer composition of claim 16, further comprising:

at least one antioxidant material.

19. The polymer composition of claim 16, wherein the additive further comprises a functional group that is reactive with the polymer matrix, the graphene, or both.

20. The polymer composition of claim 19, wherein at least a portion of the metal particles are covalently bonded to the polymer matrix, the graphene, or both.

21. The polymer composition of claim 16, wherein the additive is selected from the group consisting of 1,3,4-thiadiazole, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 1,2,4-triazole-3-thiol, 1-pyrollidinecarbodithioic acid, 2,2′

-dithiobis(benzothiazole), 2,4-dimercapto-6-amino-5-triazine, 2,4-dithiohydantoin, 2,5-dimethylbenzothiazole, 2-amino-1,3,4-thiadiazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidizole, 2-mercaptobenzoxazole, 2-mercaptoethane sulfonic acid, 2-mercaptoimidazole, 2-mercaptothiazoline, 2-thiouracil, 3-amino-5-mercapto-1,2,4-triazole, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, 5-amino-1,3,4-thiadiazole, 6-amino-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-mercaptopurine, N-cycloalkyl-dithiocarbamates, alkyl- and cycloalkyl mercaptans, benzothiazoles, dimercaptopyridines, dimethyldithiocarbamic acid, dithiocyanuric acid, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptoethanesulfonic acid, mercaptoimidazoles, mercaptopyridines, mercaptopyrimidines, mercaptoquinolines, mercaptothiazoles, mercaptothiazolines, mercaptotriazoles, O,O-dialkyl- and O,O-dicycloalkyldithiophosphates, O-alkyl- or O-cycloalkyldithiocarbonates, o-ethylxanthic acid, quinoxaline-2,3-thiol, thioacetic acid, thiocresol, thiosalicylic acid, trithiocyanuric acid, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzothiazole, diethyldithiocarbamic acid, 5-amino-1,3,4,-thiadiazole-2-thiol, 1,2,3-benzothiazole, 1-pyrollidinecarbodithioic acid, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methylbenzimidazole, mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, trithiocyanuric acid, 2,4-dithiohydantoin, 2,4-dimercapto-6-amino-5-triazine, silanes, silanols, derivatives thereof, and mixtures thereof.

22. The polymer composition of claim 16, wherein the metal particles comprise metal nanoparticles that are at most about 100 nm in size.

23. The polymer composition of claim 16, wherein the metal particles comprise metal nanoparticles that are at most about 20 nm in size.

24. The polymer composition of claim 16, wherein the polymer composition has a sheet resistivity of less than about 0.01 ohm/square.

25. A method for making an electrically conductive polymer composition, the method comprising:

reacting a graphene having a carbon;

oxygen ratio of at least about 20;

1 with a thermoplastic material to form covalent bonds therebetween; and

after reacting, adding metal particles to the thermoplastic material;

1) wherein the metal particles have an additive covalently bonded thereto;

2) the additive comprises a thiol, a silane, a silanol, a monodentate amine, a bidentate amine, or any combination thereof and

     3) a combined concentration of the metal particles and the graphene in the thermoplastic material exceeds an electrical percolation threshold.

26. The method of claim 25, wherein adding metal particles to the thermoplastic material comprises blending the metal particles with the thermoplastic material.

27. The method of claim 25, wherein the thermoplastic material comprises a polymer selected from the group consisting of polyacrylic acid, polyacrylates, polymethacrylic acid, polymethacrylates, polyvinyl alcohol, polyvinyl acetate, polycarbonates, acrylic acid copolymers, acrylate copolymers, methacrylic acid copolymers, methacrylate copolymers, vinyl alcohol copolymers, vinyl acetate copolymers, styrene copolymers, derivatives thereof, and combinations thereof.

28. The method of claim 25, further comprising:

adding at least one antioxidant material to the thermoplastic material.

29. The method of claim 25, wherein the additive is selected from the group consisting of 1,3,4-thiadiazole, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 1,2,4-triazole-3-thiol, 1-pyrollidinecarbodithioic acid, 2,2′

-dithiobis(benzothiazole), 2,4-dimercapto-6-amino-5-triazine, 2,4-dithiohydantoin, 2,5-dimethylbenzothiazole, 2-amino-1,3,4-thiadiazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidizole, 2-mercaptobenzoxazole, 2-mercaptoethane sulfonic acid, 2-mercaptoimidazole, 2-mercaptothiazoline, 2-thiouracil, 3-amino-5-mercapto-1,2,4-triazole, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, 5-amino-1,3,4-thiadiazole, 6-amino-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-mercaptopurine, N-cycloalkyl-dithiocarbamates, alkyl- and cycloalkyl mercaptans, benzothiazoles, dimercaptopyridines, dimethyldithiocarbamic acid, dithiocyanuric acid, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptoethanesulfonic acid, mercaptoimidazoles, mercaptopyridines, mercaptopyrimidines, mercaptoquinolines, mercaptothiazoles, mercaptothiazolines, mercaptotriazoles, O,O-dialkyl- and O,O-dicycloalkyldithiophosphates, O-alkyl- or O-cycloalkyldithiocarbonates, o-ethylxanthic acid, quinoxaline-2,3-thiol, thioacetic acid, thiocresol, thiosalicylic acid, trithiocyanuric acid, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzothiazole, diethyldithiocarbamic acid, 5-amino-1,3,4,-thiadiazole-2-thiol, 1,2,3-benzothiazole, 1-pyrollidinecarbodithioic acid, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methylbenzimidazole, mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, trithiocyanuric acid, 2,4-dithiohydantoin, 2,4-dimercapto-6-amino-5-triazine, silanes, silanols, derivatives thereof, and mixtures thereof.

30. The method of claim 25, wherein the additive further comprises a functional group that is reactive with the thermoplastic material, the graphene, or both.

31. The method of claim 30, further comprising:

reacting the metal particles with the graphene, the thermoplastic material, or both so as to form covalent bonds therebetween.

32. The method of claim 25, wherein the metal particles comprise metal nanoparticles that are at most about 100 nm in size.

33. The method of claim 25, wherein the metal particles comprise metal nanoparticles that are at most about 20 nm in size.

34. A method for forming a connection, the method comprising:

heating a solder material to at least its softening temperature;

wherein the solder material comprises an electrically conductive polymer composition that comprises a thermoplastic material, a graphene that is covalently bonded to the thermoplastic material, and metal particles;

placing at least one member in the softened solder material; and

cooling the softened solder material so as to affect hardening and to affix the at least one member thereto.

35. The method of claim 34, wherein the solder material is reworkable after being cooled into a hardened state.

36. A method for reworking a connection, the method comprising:

heating a connection comprising at least one member and a solder material to at least a softening temperature of the solder material;

wherein the solder material comprises an electrically conductive polymer composition that comprises a thermoplastic material, a graphene that is covalently bonded to the thermoplastic material, and metal particles; and

removing the at least one member from the connection.

37. The method of claim 36, further comprising:

adding at least one replacement member to the softened solder material.

38. The method of claim 36, further comprising:

removing the softened solder material from the connection.

39. The method of claim 38, further comprising:

adding a fresh solder material to the connection;

wherein the fresh solder material comprises an electrically conductive polymer composition that comprises a thermoplastic material, a graphene that is covalently bonded to the thermoplastic material, and metal particles;

heating the fresh solder material to at least its softening temperature;

placing at least one replacement member in the softened, fresh solder material; and

cooling the softened, fresh solder material so as to affect hardening and to affix the at least one replacement member thereto.

40. A polymer composition comprising:

a polymer matrix;

a graphene that is covalently bonded to the polymer matrix; and

metal particles having an additive covalently bonded thereto;

wherein the additive is selected from the group consisting of 1,3,4-thiadiazole, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 1,2,4-triazole-3-thiol, 1-pyrollidinecarbodithioic acid, 2,2′

-dithiobis(benzothiazole), 2,4-dimercapto-6-amino-5-triazine, 2,4-dithiohydantoin, 2,5-dimethylbenzothiazole, 2-amino-1,3,4-thiadiazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidizole, 2-mercaptobenzoxazole, 2-mercaptoethane sulfonic acid, 2-mercaptoimidazole, 2-mercaptothiazoline, 2-thiouracil, 3-amino-5-mercapto-1,2,4-triazole, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, 5-amino-1,3,4-thiadiazole, 6-amino-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-mercaptopurine, N-cycloalkyl-dithiocarbamates, alkyl- and cycloalkyl mercaptans, benzothiazoles, dimercaptopyridines, dimethyldithiocarbamic acid, dithiocyanuric acid, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptoethanesulfonic acid, mercaptoimidazoles, mercaptopyridines, mercaptopyrimidines, mercaptoquinolines, mercaptothiazoles, mercaptothiazolines, mercaptotriazoles, O,O-dialkyl- and O,O-dicycloalkyldithiophosphates, O-alkyl- or O-cycloalkyldithiocarbonates, o-ethylxanthic acid, quinoxaline-2,3-thiol, thioacetic acid, thiocresol, thiosalicylic acid, trithiocyanuric acid, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzothiazole, diethyldithiocarbamic acid, 5-amino-1,3,4,-thiadiazole-2-thiol, 1,2,3-benzothiazole, 1-pyrollidinecarbodithioic acid, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methylbenzimidazole, mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, trithiocyanuric acid, 2,4-dithiohydantoin, 2,4-dimercapto-6-amino-5-triazine, silanes, silanols, derivatives thereof, and mixtures thereof;

wherein a combined concentration of the metal particles and the graphene in the polymer matrix exceeds an electrical percolation threshold.

41. A method for making an electrically conductive polymer composition, the method comprising:

reacting a graphene having a carbon;

oxygen ratio of at least about 20;

1 with a thermoplastic material to form covalent bonds therebetween; and

after reacting, adding metal particles to the thermoplastic material;

wherein the metal particles have an additive covalently bonded thereto;

wherein the additive is selected from the group consisting of 1,3,4-thiadiazole, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 1,2,4-triazole-3-thiol, 1-pyrollidinecarbodithioic acid, 2,2′

-dithiobis(benzothiazole), 2,4-dimercapto-6-amino-5-triazine, 2,4-dithiohydantoin, 2,5-dimethylbenzothiazole, 2-amino-1,3,4-thiadiazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidizole, 2-mercaptobenzoxazole, 2-mercaptoethane sulfonic acid, 2-mercaptoimidazole, 2-mercaptothiazoline, 2-thiouracil, 3-amino-5-mercapto-1,2,4-triazole, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, 5-amino-1,3,4-thiadiazole, 6-amino-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-mercaptopurine, N-cycloalkyl-dithiocarbamates, alkyl- and cycloalkyl mercaptans, benzothiazoles, dimercaptopyridines, dimethyldithiocarbamic acid, dithiocyanuric acid, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptoethanesulfonic acid, mercaptoimidazoles, mercaptopyridines, mercaptopyrimidines, mercaptoquinolines, mercaptothiazoles, mercaptothiazolines, mercaptotriazoles, O,O-dialkyl- and O,O-dicycloalkyldithiophosphates, O-alkyl- or O-cycloalkyldithiocarbonates, o-ethylxanthic acid, quinoxaline-2,3-thiol, thioacetic acid, thiocresol, thiosalicylic acid, trithiocyanuric acid, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzothiazole, diethyldithiocarbamic acid, 5-amino-1,3,4,-thiadiazole-2-thiol, 1,2,3-benzothiazole, 1-pyrollidinecarbodithioic acid, 1-(4-hydroxyphenyl)-1H-tetrazol-5-thiol, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-methylbenzimidazole, mercaptobenzothiazoles, mercaptothiazolines, mercaptobenzimidazoles, 5,5-dithio-bis(1,3,4-thiadiazole-2(3H)-thione, trithiocyanuric acid, 2,4-dithiohydantoin, 2,4-dimercapto-6-amino-5-triazine, silanes, silanols, derivatives thereof, and mixtures thereof; and

wherein a combined concentration of the metal particles and the graphene in the thermoplastic material exceeds an electrical percolation threshold.