Photopolymer resins with solid and liquid phases for polymer-derived ceramics

Patent metadata

Field	Value
Publication number	US-10590042-B2
Application number	US-201815946680-A
Country	US
Kind code	B2
Filing date	Apr 5, 2018
Priority date	Jun 29, 2017
Publication date	Mar 17, 2020
Grant date	Mar 17, 2020

Abstract

Resins for 3D printing of a preceramic composition loaded with a solid polymer filler, followed by converting the preceramic composition to a 3D-printed ceramic material, are described. Some variations provide a preceramic composition containing a radiation-curable liquid resin formulation and a solid polymer filler dispersed within the liquid resin formulation. The liquid resin formulation is compatible with stereolithography, UV curing, and/or 3D printing. The solid polymer filler may be an organic polymer, an inorganic polymer, or a combination thereof. The solid polymer filler may itself be an inorganic preceramic polymer, which may have the same composition as a polymerized variant of the liquid resin formulation, or a different composition. Many compositions are disclosed as options for the liquid resin formulation and the solid polymer filler.

First claim

What is claimed is:

1. A preceramic composition containing (a) a UV-curable inorganic liquid resin formulation, (b) a solid polymer filler dispersed within said UV-curable inorganic liquid resin formulation, and (c) a photoinitiator, wherein said UV-curable inorganic liquid resin formulation is capable of being polymerized when exposed to said photoinitiator and electromagnetic radiation wavelengths selected from 200 nm to 700 nm, wherein said solid polymer filler is selected from the group consisting of poly(carbosilanes), poly(silazanes), poly(silsesquioxanes), poly(borosiloxanes), poly(borosilanes), poly(borosilazanes), poly(carbosiloxanes), poly(silylcarboimides), poly(silsesquicarbodiimides), polyborazines, and combination thereof.

2. The preceramic composition of claim 1 , wherein said electromagnetic radiation wavelengths are selected from 200 nm to 500 nm.

3. The preceramic composition of claim 1 , wherein said solid polymer filler is present at a concentration from about 0.1 vol % to about 95 vol % of said preceramic composition.

4. The preceramic composition of claim 3 , wherein said solid polymer filler is present at a concentration from about 1 vol % to about 70 vol % of said preceramic composition.

5. The preceramic composition of claim 1 , wherein said solid polymer is characterized by a pyrolysis temperature equal to, or greater than, the pyrolysis temperature of a polymer of said UV-curable inorganic liquid resin formulation.

6. The preceramic composition of claim 1 , wherein said solid polymer is characterized by a pyrolysis temperature less than the pyrolysis temperature of a polymer of said UV-curable inorganic liquid resin formulation.

7. The preceramic composition of claim 1 , wherein said solid polymer filler is itself an inorganic preceramic polymer.

8. The preceramic composition of claim 7 , wherein said solid polymer filler has the same composition as a polymer of said UV-curable inorganic liquid resin formulation.

9. The preceramic composition of claim 7 , wherein said solid polymer filler has a different composition than a polymer of said UV-curable inorganic liquid resin formulation.

10. The preceramic composition of claim 1 , wherein a surface of said solid polymer filler is modified to aid dispersion of said solid polymer filler within said UV-curable inorganic liquid resin formulation.

11. The preceramic composition of claim 1 , said preceramic composition further comprising a surfactant or dispersion agent.

12. The preceramic composition of claim 1 , said preceramic composition further comprising a solid metal filler and/or a solid ceramic filler.

13. The preceramic composition of claim 12 , wherein said preceramic composition comprises a solid metal filler that has a melting temperature equal to, or greater than, the pyrolysis temperature of said UV-curable inorganic liquid resin formulation when in polymerized form.

14. The preceramic composition of claim 12 , wherein said preceramic composition comprises a solid metal filler that has a melting temperature less than the pyrolysis temperature of said UV-curable inorganic liquid resin formulation when in polymerized form.

15. A preceramic composition containing (a) a UV-curable inorganic liquid resin formulation, (b) a solid polymer filler dispersed within said UV-curable inorganic liquid resin formulation, and (c) a photoinitiator, wherein said UV-curable inorganic liquid resin formulation is capable of being polymerized when exposed to said photoinitiator and electromagnetic radiation wavelengths selected from 200 nm to 700 nm, wherein said solid polymer filler is itself an inorganic preceramic polymer that has the same composition as a polymer of said UV-curable inorganic liquid resin formulation.

16. A preceramic composition containing (a) a UV-curable inorganic liquid resin formulation, (b) a solid polymer filler dispersed within said UV-curable inorganic liquid resin formulation, and (c) a photoinitiator, wherein said UV-curable inorganic liquid resin formulation is capable of being polymerized when exposed to said photoinitiator and electromagnetic radiation wavelengths selected from 200 nm to 700 nm, wherein said solid polymer filler is a boron-based polymer.

Assignees

• Hrl Lab Llc

Inventors

• Eckel Zak C
• Hundley Jacob M
• Mone Robert

Classifications

• C04B2235/486

  Boron containing organic compounds, e.g. borazine, borane or boranyl · CPC title

• C04B35/63452

  Polyepoxides · CPC title

• C04B2235/483

  Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes · CPC title

• C04B35/597

  based on silicon oxynitride, {e.g. SIALONS} · CPC title

• C08G77/28

  sulfur-containing groups · CPC title