Electrically conductive ink for solvent-cast 3D printing

• US 10,647,057 B2
• Filed: 07/19/2017
• Issued: 05/12/2020
• Est. Priority Date: 07/20/2016
• Status: Expired due to Fees

• Current Assignee: Polyvalor LP
• Original Assignee: Polyvalor LP
• Inventors: Therriault, Daniel, Chizari, Kambiz
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/654,094
• Publication Number:
  US 20180022023A1
• Time in Patent Office: 1,028 Days
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/153 using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• CPC Class Codes: B29K 2995/0005 Conductive
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C07C 19/03 Chloromethanes
• CPC Class Codes: C07C 307/08 having nitrogen atoms of the sulfamide groups bound to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C07C 31/02 Monohydroxylic acyclic alcohols
• CPC Class Codes: C08B 37/003 Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C08L 5/08 Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
• CPC Class Codes: C09D 105/08 Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C09D 7/61 inorganic
• CPC Class Codes: C09D 7/70 characterised by shape, e.g. fibres, flakes or microspheres

Abstract

An ink for solvent-cast 3D printing is provided. The ink comprises a solution or gel of a polymer in a volatile solvent, and carbon nanotubes dispersed in the solution or gel. In the ink, the carbon nanotubes are present in a carbon nanotubes:polymer weight ratio between about 20:80 and about 40:60, and the polymer and carbon nanotubes total concentration is between about 20 and about 35 wt %, based on the total weight of the ink. There is also provided a 3D printer ink cartridge comprising the ink; a method of manufacturing the ink; a method of manufacturing a solvent-cast 3D printed material using the ink, a solvent-cast 3D printed material as well as uses thereof.

Claims

1. An ink for solvent-cast 3D printing, the ink comprising:

a solution or a gel of a polymer in a volatile solvent, and

carbon nanotubes dispersed in the solution or gel,

wherein the carbon nanotubes are present in a carbon nanotubes;

polymer weight ratio between about 20;

80 and about 40;

60,

wherein the polymer and carbon nanotubes total concentration is between about 20 and about 35 wt %, based on the total weight of the ink, and

wherein the volatile solvent is a solvent that evaporates at room temperature.

2. The ink of claim 1, wherein the polymer and carbon nanotubes total concentration is between about 25 and about 30 wt %, based on the total weight of the ink.

3. The ink of claim 1, wherein the polymer is poly(lactic acid), polystyrene, poly(methyl acrylate), poly(methyl methacrylate), poly(n-butyl acrylate), poly(2-hydroxyethyl methacrylate), poly(glycidyl methacrylate), poly(acrylic acid), poly(N-N-dimethylacrylamide), poly(1-vinyl anthracene), poly(2-vinyl pyridine), poly(4-vinyl pyridine), poly(N-vinyl carbazole), poly(N-vinyl carbazole), poly(N-vinyl imidazole), poly(vinyl benzyl chloride), poly(4-vinyl benzoic acid), poly(vinyl acetate), polycaprolactone, poly(11-[4-(4-butylphenylazo)phenoxy]-undecyl methacrylate) (poly(AzoMA)), poly(ferrocenyldimethylsilane), polyisoprene, polybutadiene, polyisobutylene, poly propylene glycol, poly(ethylene glycol), a polysaccharide, or a mixture thereof.

4. The ink of claim 3, wherein the polysaccharide is chitosan.

5. The ink of claim 1, wherein the solvent is dichloromethane (DCM), chloroform (CHCl₃), tetrahydrofuran (THF), acetone, methanol (MeOH), ethanol (EtOH), or water.

6. The ink of claim 1, wherein the ink further comprises one or more additive.

7. The ink of claim 1, wherein the carbon nanotubes are single-wall carbon nanotubes or multiwall carbon nanotubes.

8. The ink of claim 1, wherein the polymer is poly(lactic acid) and the solvent is dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, or ethanol.

9. The ink of claim 8, wherein the solvent is dichloromethane.

10. The ink of claim 1, wherein the polymer is chitosan, the solvent is water, and the solution or gel of the polymer in the volatile solvent is a chitosan hydrogel.

11. The ink of claim 10, wherein the ink further comprises one or more weak organic acid.

12. The ink of claim 11, wherein the ink comprises 70 vol % acetic acid alone or together with 10 vol % lactic acid and 3 wt % citric acid, the vol % being based on the total volume of the water and acids and the wt % being based on the total weight of the water and acids.

13. A method of manufacturing the solvent-cast 3D printing ink of claim 1, the method comprising the steps of:

a) providing a solution or a gel of a polymer in a solvent,

b) providing carbon nanotubes in a carbon nanotubes;

polymer weight ratio of between about 20;

80 and about 40;

60,

c) dispersing the carbon nanotubes in the solution or gel of the polymer by ball milling, thereby producing the ink, and

d) avoid drying the ink, thus keeping the solvent in the ink, until the ink is used for solvent-cast 3D printing.

14. The method of claim 13, wherein the concentration of the polymer in the solution or gel of step a) is between about 2 wt % and about 15 wt %, based on the total weight of the solution or gel.

15. The method of claim 13, wherein the ball milling in step c) is carried out for 10 to 30 minutes.

16. The method of claim 13, further comprising, before or after step d), the step of adding solvent, or removing part of the solvent so that the polymer and carbon nanotubes total concentration in the ink is between about 20 and about 35 wt %, based on the total weight of the ink.

17. The method of claim 13, further comprising the step of adding one or more additives to the solvent, to the solution or gel of the polymer, or to the ink.

18. The method of claim 13, further comprising the step of packaging the ink in a 3D printer ink cartridge.

19. A method of using the solvent-cast 3D printing ink of claim 1 for manufacturing a solvent-cast 3D printed material, the method comprising the steps of:

a) providing the solvent-cast 3D printing ink claim 1;

b) using a 3D printer, extruding the ink through a needle into a controlled pattern; and

c) allowing solvent evaporation, thereby providing the solvent-cast 3D printed material.