Thermosetting composite material and associated printing method

Patent metadata

Field	Value
Publication number	US-2023347584-A1
Application number	US-202117794948-A
Country	US
Kind code	A1
Filing date	Jan 26, 2021
Priority date	Jan 28, 2020
Publication date	Nov 2, 2023
Grant date	—

Abstract

A thermosetting composite material and its method for 3D printing by extrusion, the thermosetting composite material including a furan polymer forming a thermosetting matrix, a solvent, and a material formed from particles chosen from among micrometric particles, nanometric particles, even a mixture of micrometric particles and nanometric particles, these particles being with the basis of a compound comprising more than 40% by mass of carbon. The thermosetting composite material and its 3D printing method enabling to obtain an object having dimensional tolerances of between 2.5 and 5% with respect to the numerical model, and a resistance to high temperatures going up to 300° C. The thermosetting composite material and its 3D printing method representing a biosourced and cheaper alternative with respect to synthetic thermoplastic polymers and their usual printing method.

First claim

1 . A thermosetting composite material for 3D printing comprising:
a furan copolymer or homopolymer, formed from furfuryl alcohol monomer or its derivatives, and forming a thermosetting matrix of the composite material, and a non-miscible material with the thermosetting matrix,
wherein that the thermosetting composite material further comprises a solvent, and in that the non-miscible material with the thermosetting matrix is formed of particles chosen from among:
micrometric particles, at least 50% of the micrometric particles having at least one dimension of between 1 and 100 m,
nanometric particles, at least 50% of the nanometric particles having at least one dimension of between 1 and 100 nm, and
a mixture of said micrometric particles and nanometric particles,

the particles being with the basis of a compound comprising more than 40% by mass of carbon, and are chosen from among graphite, carbon black, graphene particles, carbon nanotubes and carbon nanofibres, a micrometric cellulose powder, nanocellulose, and particles with the basis of one from among sawdust and fruit pips or shells,
when the particles are chosen from among graphite, carbon black, graphene particles, carbon nanotubes or carbon nanofibres, the proportion of particles in the thermosetting composite material is of between 10% and 70% with respect to the total mass of the composite material,
when the particles are chosen from among a micrometric cellulose powder and nanocellulose, the proportion of particles in the thermosetting composite material is of between 15% and 40% by mass, with respect to the total mass of the composite material,
when the particles are with the basis of one from among sawdust, fruit pips and shells, the proportion of particles in the thermosetting composite material is of between 10% and 80% by mass, with respect to the total mass of the composite material.

2 . The thermosetting composite material according claim 1 , wherein, when the particles are chosen from among a micrometric cellulose powder and nanocellulose, the proportion of particles in the thermosetting composite material is of between 20% and 35%, and more preferably, between 25% and 30%, with respect to the total mass of the composite material.

3 . The thermosetting composite material according to claim 1 , wherein, when the particles are with the basis of one from among sawdust, fruit pips and shells, the proportion of particles in the thermosetting composite material is of between 15% and 60%, and more preferably between 20% and 40%, with respect to the total mass of the composite material.

4 . The thermosetting composite material according to claim 1 , wherein, when the particles are carbon particles, the proportion of particles in the thermosetting composite material ( 1 ) is of between 40% and 60%, with respect to the total mass of the composite material.

5 . The thermosetting composite material according to claim 1 , wherein the proportion of the solvent in the thermosetting composite material is of between 5% and 25% by mass, preferably between 10% and 20%, with respect to the total mass of the composite material.

6 . The thermosetting composite material according to claim 1 , wherein the solvent has at least one from among a boiling point of less than 150° C. and a flashpoint temperature of greater than 50° C.

7 . The thermosetting composite material according to claim 1 , wherein the solvent is chosen from among water, ethanol, isopropanol and a mixture of at least two from among water, ethanol and isopropanol.

8 . The thermosetting composite material according to claim 1 , wherein the proportion of the furan polymer in the thermosetting composite material is greater than 20% by mass, preferably the proportion of the furan polymer is of between 50% and 70% by mass, with respect to the total mass of the composite material.

9 . The thermosetting composite material according to claim 1 , wherein the furan polymer has a polymerisation degree of less than 10, and preferably the furan polymer is non-cross-linked.

10 . An use of a thermosetting composite material according to claim 1 , for 3D printing by extrusion.

11 . A method for the 3D printing of an object, comprising:
an extrusion of a thermosetting composite material according to claim 1 , wherein the thermosetting composite material is extruded at an extrusion temperature greater than or equal to the ambient temperature T amb and less than the cross-linking temperature T ret of the furan polymer, and a heat treatment comprising an annealing of the extruded thermosetting composite material, at an annealing temperature T 2 greater than or equal to the cross-linking temperature T ret ) of the furan polymer, so as to induce an at least partial cross-linking of the thermosetting matrix to form an object in a thermoset composite material comprising an at least partially cross-linked matrix.

12 . The method according claim 11 , wherein the heat treatment further comprises, before the annealing of the extruded thermosetting composite material, an intermediate annealing of the extruded thermosetting composite material, at at least one intermediate annealing temperature T 3 of between the extrusion temperature T 1 and the cross-linking temperature T ret of the furan polymer, so as to at least partially evaporate the solvent of the thermosetting composite material before the cross-linking of the thermosetting matrix.

13 . The method according claim 12 , wherein, the intermediate annealing temperature T 3 is of between 40° C. and 90° C.

14 . The method according to claim 11 , wherein, the annealing temperature T 2 is of between 90° C. and 200° C., preferably between 100° C. and 150° C.

15 . The method according to claim 11 , wherein, during the extrusion, the thermosetting composite material is extruded by a printing nozzle, the printing nozzle having a diameter of between 0.2 and 2 mm.

16 . The method according to claim 11 , wherein, during the extrusion, the thermosetting composite material is extruded at a speed V of between 10 mm/s and 50 mm/s.

17 . The method according to claim 11 , wherein, during the extrusion, the thermosetting composite material is extruded under a pressure greater than 3 bar.

Assignees

• Inst Polytechnique Grenoble
• Centre Nat Rech Scient

Inventors

• Beneventi David
• Chaussy Didier
• Bouzidi Khaoula
• Gandini Alessandro

Classifications

• B29C64/165 Primary

  using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B29K2401/00

  Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as filler · CPC title

• C08G61/125 Primary

  with a five-membered ring containing one oxygen atom in the ring · CPC title