Photo-curable liquid composition for additive manufacturing of ceramic

Patent metadata

Field	Value
Publication number	US-12043748-B2
Application number	US-202017030475-A
Country	US
Kind code	B2
Filing date	Sep 24, 2020
Priority date	Sep 24, 2020
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

A photo-curable liquid composition for additive manufacturing of silicon-containing carbide ceramic includes a polymethylvinylsilane (PMVS) resin that has photo-reactivity over a first photo-wavelength absorption range and a photo-initiator additive mixed with the PMVS resin. The photo-initiator additive has photo-reactivity over a second photo-wavelength absorption range that has an overlapping wavelength range with the first photo-wavelength absorption range. The PMVS and the photo-initiator additive are reactive to polymerize upon exposure to radiation having a wavelength in the overlapping wavelength range.

First claim

What is claimed is:

1. A photo-curable liquid composition for additive manufacturing of silicon-containing carbide ceramic, the composition comprising a polymethylvinylsilane (PMVS) resin having photo-reactivity over a first photo-wavelength absorption range and a photo-initiator additive mixed with the PMVS resin, the photo-initiator additive having photo-reactivity over a second photo-wavelength absorption range that has an overlapping wavelength range with the first photo-wavelength absorption range, the PMVS and the photo-initiator additive of the composition being reactive to polymerize upon exposure to radiation having a wavelength in the overlapping wavelength range and wherein a vinyl group of the PMVS is in an allyl group.

2. The composition as recited in claim 1 , wherein the photo-initiator additive is selected from the group consisting of benzoin ethers, benzil ketals, alpha-dialkoxy-aceto-phenones, alpha-hydroxyl-alkyl-phenones, alpha-amino-alkyl-phenones, acyl-phosphine oxides, benzo-phenones/amines, thio-xanthones/amines, titanocenes, and combinations thereof.

3. The composition as recited in claim 1 , wherein the photo-initiator additive is selected from the group consisting of 1-hydroxycyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropanone, bis-acyl-phosphine oxide, benzophenone and its derivatives, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.

4. The composition as recited in claim 1 , wherein the PMVS further comprises an acryloyl group.

5. The composition as recited in claim 1 , wherein the PMVS has, by molar percent, from 5 to 50 of allyl groups.

6. The composition as recited in claim 1 , wherein the composition has, in parts by weight, from 25 to 99.9 of the PMVS resin and from 0.1 to 10 of the photo-initiator additive.

7. The composition as recited in claim 6 , wherein the composition further comprises a viscosity modifier selected from the group consisting of low molecular weight versions of the PMVS resin, compatible solvents, oligomeric material, functionalized monomeric compounds or combinations thereof.

8. The composition as recited in claim 7 , wherein the composition has, in parts by weight, from 2 to 40 of the viscosity modifier.

9. A photo-curable liquid composition for additive manufacturing of silicon-containing carbide ceramic, the composition comprising:
90 to 99.9 parts by weight of a polymethylvinylsilane (PMVS) resin, wherein a vinyl group of the PMVS is in an allyl group; and
0.1 to 10 parts by weight of a photo-initiator additive mixed with the PMVS resin.

10. The composition as recited in claim 9 , wherein the photo-initiator additive is selected from the group consisting of benzoin ethers, benzil ketals, alpha-dialkoxy-aceto-phenones, alpha-hydroxyl-alkyl-phenones, alpha-amino-alkyl-phenones, acyl-phosphine oxides, benzo-phenones/amines, thio-xanthones/amines, titanocenes, and combinations thereof.

11. The composition as recited in claim 10 , wherein the PMVS comprises an acryloyl group, and the PMVS has, by molar percent, from 5 to 50 of acryloyl groups.

12. The composition as recited in claim 10 , wherein a vinyl group of the PMVS is in an allyl group, and the PMVS has, by molar percent, from 5 to 50 of allyl groups.

13. The composition as recited in claim 10 , wherein the PMVS has, by molar percent, from 10 to 95 of vinyl groups.

14. The composition as recited in claim 9 , wherein the composition further comprises a viscosity modifier selected from the group consisting of low molecular weight versions of the PMVS resin, compatible solvents, oligomeric material, functionalized monomeric compounds or combinations thereof, and the composition has, in parts by weight, from 2 to 40 of the viscosity modifier.

15. The composition as recited in claim 9 , wherein the PMVS has photo-reactivity over a first photo-wavelength absorption range, and the photo-initiator additive has photo-reactivity over a second photo-wavelength absorption range that has an overlapping wavelength range with the first photo-wavelength absorption range, the PMVS and the photo-initiator additive being reactive to polymerize upon exposure to radiation having a wavelength in the overlapping wavelength range.

16. A photo-curable liquid composition for additive manufacturing of silicon-containing carbide ceramic, the composition comprising a polymethylvinylsilane (PMVS) resin having photo-reactivity over a first photo-wavelength absorption range and a photo-initiator additive mixed with the PMVS resin, the photo-initiator additive having photo-reactivity over a second photo-wavelength absorption range that has an overlapping wavelength range with the first photo-wavelength absorption range, the PMVS and the photo-initiator additive of the composition being reactive to polymerize upon exposure to radiation having a wavelength in the overlapping wavelength range.

17. The composition as recited in claim 1 , wherein the photo-initiator additive is selected from the group consisting of alpha-amino-alkyl-phenones, acyl-phosphine oxides, benzo-phenones/amines, thio-xanthones/amines, titanocenes, and combinations thereof.

18. The composition as recited in claim 1 , wherein the photo-initiator additive is selected from the group consisting of 1-hydroxycyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropanone, bis-acyl-phosphine oxide, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.

19. The composition as recited in claim 1 , wherein the PMVS resin has a chemical formula of:

20. The composition as recited in claim 1 , wherein the PMVS resin has a chemical formula of:

Assignees

• Raytheon Tech Corp
• Rtx Corp

Inventors

• Schmidt Wayde R

Classifications

• C09D11/102

  containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• B29K2083/00

  Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material · CPC title

• B28B1/001

  Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00) · CPC title

• C01B32/977

  Preparation from organic compounds containing silicon · CPC title