Monomer formulations and methods for 3D printing of preceramic polymers

Patent metadata

Field	Value
Publication number	US-11535568-B2
Application number	US-201715822199-A
Country	US
Kind code	B2
Filing date	Nov 26, 2017
Priority date	Nov 30, 2016
Publication date	Dec 27, 2022
Grant date	Dec 27, 2022

Abstract

This invention provides resin formulations which may be used for 3D printing and pyrolyzing to produce a ceramic matrix composite. The resin formulations contain a solid-phase filler, to provide high thermal stability and mechanical strength (e.g., fracture toughness) in the final ceramic material. The invention provides direct, free-form 3D printing of a preceramic polymer loaded with a solid-phase filler, followed by converting the preceramic polymer to a 3D-printed ceramic matrix composite with potentially complex 3D shapes or in the form of large parts. Other variations provide active solid-phase functional additives as solid-phase fillers, to perform or enhance at least one chemical, physical, mechanical, or electrical function within the ceramic structure as it is being formed as well as in the final structure. Solid-phase functional additives actively improve the final ceramic structure through one or more changes actively induced by the additives during pyrolysis or other thermal treatment.

First claim

What is claimed is:

1. A preceramic monomer formulation for 3D-printing and free-radical polymerization, said monomer formulation comprising:
(a) from 3 wt % to 97 wt % of a monomer molecule containing (i) non-carbon atoms and (ii) two or more C═X double bonds, two or more C≡X triple bonds, or at least one C═X double bond and at least one C≡X triple bond, wherein X is selected from C, S, N, O, or a combination thereof, wherein said monomer molecule includes two or more functional groups selected from the group consisting of vinyl ether, vinyl ester, vinyl amide, vinyl triazine, vinyl isocyanurate, acrylate, methacrylate, and combinations thereof, wherein said monomer molecule does not include a functional group consisting of a pure vinyl group, wherein said pure vinyl group is not part of a vinyl ether group, a vinyl ester group, a vinyl amide group, a vinyl triazine group, or a vinyl isocyanurate group, and wherein said two or more functional groups are selected for free-radical polymerization;
(b) a photoinitiator that generates free radicals by intramolecular bond cleavage or intermolecular hydrogen abstraction when exposed to light having a wavelength from about 200 nm to about 500 nm, wherein said photoinitiator is selected for free-radical polymerization, and wherein said photoinitiator is present in a concentration from about 0.001 wt % to about 10 wt % in said formulation;
(c) a free-radical inhibitor that inhibits free-radical polymerization, wherein said free-radical inhibitor is present in a concentration from about 0.001 wt % to about 10 wt % in said formulation;
(d) a thermal free-radical initiator, wherein said thermal free-radical initiator is present in a concentration from about 0.001 wt % to about 10 wt % in said formulation; and
(e) a 3D-printing resolution agent selected from the group consisting of UV absorbers, fluorescent molecules, optical brighteners, and combinations thereof, wherein said 3D-printing resolution agent is present in a concentration from about 0.001 wt % to about 10 wt % in said formulation,
wherein said preceramic monomer formulation does not include a functional group consisting of a thiol group.

2. The formulation of claim 1 , wherein said non-carbon atoms are selected from the group consisting of Si, B, Al, Ti, Zn, P, S, Ge, and combinations thereof.

3. The formulation of claim 1 , wherein at least one of said C═X double bonds or said C≡X triple bonds is located at a terminal position of said monomer molecule.

4. The formulation of claim 1 , wherein said two or more functional groups are selected from the group consisting of acrylate, methacrylate, and combinations thereof.

5. The formulation of claim 1 , wherein said monomer molecule contains an alkyl group, an ester group, an amine group, a hydroxyl group, or a combination thereof.

6. The formulation of claim 1 , wherein said X is selected from C, S, or a combination thereof.

7. The formulation of claim 1 , wherein at least 10 wt % of said monomer molecule is inorganic.

8. The formulation of claim 1 , wherein at least 10% (on an atom basis) of said non-carbon atoms is Si.

9. The formulation of claim 1 , wherein said photoinitiator is present in a concentration from about 0.001 wt % to about 10 wt % in said formulation.

10. The formulation of claim 1 , wherein said photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, camphorquinone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, benzophenone, benzoyl peroxide, and combinations thereof.

11. The formulation of claim 1 , wherein said thermal free-radical initiator is selected from the group consisting of benzoyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, and combinations thereof.

12. The formulation of claim 1 , wherein said formulation further includes a radiation-trigger free-radical initiator active at a second wavelength that is substantially different from a first wavelength for which said photoinitiator is active.

13. The formulation of claim 1 , wherein said free-radical inhibitor is selected from the group consisting of hydroquinone, methylhydroquinone, ethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone, monomethylether hydroquinone, propylhydroquinone, propoxyhydroquinone, tert-butylhydroquinone, n-butylhydroquinone, and combinations thereof.

14. The formulation of claim 1 , wherein said 3D-printing resolution agent is selected from the group consisting of 2-(2-hydroxyphenyl)-benzotriazole, 2-hydroxyphenyl-benzophenones, 2-hydroxyphenyl-s-triazines, thiophenediyl)bis(5-tert-butylbenzoxazole), 2,2′-(1,2-ethenediyl)bis(4,1-phenylene)bisbenzoxazole, and combinations thereof.

15. The formulation of claim 1 , wherein said formulation further comprises from about 0.1 vol % to about 70 vol % of solid-phase fillers.

Assignees

• Hrl Lab Llc

Inventors

• Eckel Zak C
• Nowak Andrew P
• Nelson Ashley M
• Rodriguez April R

Classifications

• B29C71/02

  Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)} · CPC title

• C04B2235/6026

  Computer aided shaping, e.g. rapid prototyping · CPC title

• C04B35/488

  Composites · CPC title

• C04B2235/96

  Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance · CPC title

• C04B35/5622

  based on zirconium or hafnium carbides · CPC title