Methods of 3D printing thermosetting polymers and continuous fiber composites via in-situ self-propagation curing and systems thereof
View Patent ↗Methods and systems of 3D printing non-photocurable thermosetting polymer materials and continuous fiber composites that reduces the manufacturing time and energy required by implementing fast, self-sustaining, and self-propagating, in-situ curing of the polymer and the and continuous fiber composites as the non-photocurable thermosetting polymer materials are being printed.
1 . A three-dimensional (3D) printing method comprising:
(a) fabricating a 3D object from a non-photocurable thermosetting material, wherein the fabrication comprises utilizing a 3D printer to extrude the non-photocurable thermosetting material and form the three-dimensional object layer-by-layer; and
(b) during fabrication of the 3D object utilizing the 3D printer, initializing an exothermic reaction that results in the in-situ polymerization of the non-photocurable thermosetting material, wherein
(i) the in-situ polymerization cures the non-photocurable thermosetting material to a thermoset polymer that does not require further curing to fabricate the 3D object comprising the thermoset polymer,
(ii) the initializing of the exothermic reaction occurs at an interface between a photocurable liquid resin and air,
(iii) the exothermic reaction occurs by the application of a light source at the interface, and
(iv) the surface of the layers of the three-dimensional object are positioned at the interface.
2 . The 3D printing method of claim 1 , wherein the non-photocurable thermosetting material is selected from a group consisting of non-photocurable thermosetting epoxy resins, non-photocurable thermosetting phenolic resins, non-photocurable thermosetting cyanate esters, benzoxazine, bismaleimide, and combinations thereof.
3 . The 3D printing method of claim 1 , wherein the application of the light source is controlled using an optical signal guide curing window.
4 . The 3D printing method of claim 1 , wherein the exothermic reaction is initiated photonically.
5 . The 3D printing method of claim 1 , wherein the exothermic reaction is a chemical reaction of the liquid resin and the air caused by the adsorption of light.
6 . The 3D printing method of claim 1 , wherein the in-situ polymerization of the non-photocurable thermosetting material is self-sustaining.
7 . The 3D printing method of claim 1 , wherein the in-situ polymerization of the non-photocurable thermosetting material is self-propagating.
8 . The 3D printing method of claim 1 , wherein the in-situ polymerization of the non-photocurable thermosetting material is self-sustaining and self-propagating.
9 . The 3D printing method of claim 1 , wherein the 3D object is selected from a group consisting of articles utilized in the aerospace, automotive, marine, energy and coating industries.
10 . The 3D printing method of claim 1 , wherein the non-photocurable thermosetting material comprises a non-photocurable thermosetting epoxy resin.
11 . The 3D printing method of claim 10 , wherein the 3D object is an article selected from a group consisting of electronic parts, motors, transformers, and generators.
12 . The 3D printing method of claim 1 , wherein the non-photocurable thermosetting material comprises a non-photocurable thermosetting phenolic resin.
13 . The 3D printing method of claim 12 , wherein the 3D object is an article selected from a group consisting of billiard balls, circuit boards, brake pads, brake shoes, and clutch discs.
14 . The 3D printing method of claim 1 , wherein the non-photocurable thermosetting material comprises a non-photocurable thermosetting cyanate ester.
15 . The 3D printing method of claim 14 , wherein the 3D object is an article selected from a group consisting of spacecrafts, aircrafts, missiles, antennae, microelectronics, and microwaves.
16 . The 3D printing method of claim 1 , wherein the 3D printing method utilizes a curing agent.
17 . The 3D printing method of claim 16 , wherein
(a) the curing agent comprises a first component and a second component, and
(b) molar ratio of the first component to the second component is at a ratio between 2:0.01 and 2:0.1.
18 . The 3D printing method of 17 , wherein the molar ratio of the first component, the second component, and the non-photocurable thermosetting material is between 2:0.01:100 and 2:0.1:100.
19 . The 3D printing method of claim 17 , wherein
(a) the first component is 1,1,2,2-tetraphenyl-1, 2-ethandiol (I-TI), and
(b) the second component is fluorinated alkoxyaluminate (I-Al).
20 . The 3D printing method of claim 16 , wherein the curing agent comprises one or both of 1,1,2,2-tetraphenyl-1, 2-ethandiol (I-TI) and fluorinated alkoxyaluminate (I-Al).
21 . The 3D printing method of claim 16 , wherein the non-photocurable thermosetting material comprises a non-photocurable thermosetting epoxy resins.
22 . The 3D printing method of claim 1 , wherein the 3D printing method utilizes a continuous fiber printing process.