Preceramic resin formulations, impregnated fibers comprising the preceramic resin formulations, and related methods

Patent metadata

Field	Value
Publication number	US-10875813-B2
Application number	US-201715819658-A
Country	US
Kind code	B2
Filing date	Nov 21, 2017
Priority date	Jul 17, 2017
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

A preceramic resin formulation comprising a polycarbosilane preceramic polymer, an organically modified silicon dioxide preceramic polymer, and, optionally, at least one filler. The preceramic resin formulation is formulated to exhibit a viscosity of from about 1,000 cP at about 25° C. to about 5,000 cP at a temperature of about 25° C. The at least one filler comprises first particles having an average mean diameter of less than about 1.0 μm and second particles having an average mean diameter of from about 1.5 μm to about 5 μm. Impregnated fibers comprising the preceramic resin formulation are also disclosed, as is a composite material comprising a reaction product of the polycarbosilane preceramic polymer, organically modified silicon dioxide preceramic polymer, and the at least one filler. Methods of forming a ceramic matrix composite are also disclosed.

First claim

What is claimed is:

1. A method of forming a ceramic matrix composite, comprising:
passing fibers through a preceramic resin formulation comprising an organically modified silicon dioxide preceramic polymer and at least one filler, the organically modified silicon dioxide preceramic polymer comprising quaternary coordinated oxygen to silicon atoms of the organically modified silicon dioxide preceramic polymer, and the preceramic resin formulation formulated to exhibit a viscosity of from about 200 cP at about 25° C. to about 5,000 cP at a temperature of about 25° C.;
impregnating the fibers with the preceramic resin formulation; and
forming the impregnated fibers into a composite material.

2. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through a preceramic resin formulation formulated to exhibit a viscosity of from about 200 cP at about 25° C. to about 5,000 cP at a temperature of about 25° C.

3. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises forming continuous fibers impregnated with the preceramic resin formulation.

4. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through a bath containing the preceramic resin formulation.

5. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises passing carbon fibers through the preceramic resin formulation.

6. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through a preceramic resin formulation comprising the organically modified silicon dioxide preceramic polymer and at least one filler comprising first particles having an average mean diameter of less than about 1.0 μm and second particles having an average mean diameter of from about 1.5 μm to about 5 μm.

7. The method of claim 6 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through the preceramic resin formulation comprising the organically modified silicon dioxide preceramic polymer and at least one of zirconium dioxide or titanium diboride.

8. The method of claim 6 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through the preceramic resin formulation comprising the organically modified silicon dioxide preceramic polymer, zirconium dioxide, and titanium diboride.

9. The method of claim 1 , wherein forming the impregnated fibers into a composite material comprises forming the composite material at a net shape.

10. The method of claim 1 , wherein forming the impregnated fibers into a composite material comprises forming the composite material at a near-net shape.

11. The method of claim 1 , wherein forming the impregnated fibers into a composite material comprises curing the impregnated fibers at a temperature of from about 121° C. to about 371° C. to form the composite material and ceramifying the composite material at a temperature of greater than about 816° C.

12. The method of claim 1 , wherein curing the impregnated fibers comprises curing the impregnated fibers at a temperature of about 371° C. and ceramifying the composite material at a temperature of about 1,093° C.

13. The method of claim 1 , wherein forming the impregnated fibers into a composite material comprises forming the composite material at a ceramic yield of greater than about 90%.

14. The method of claim 1 , wherein forming the impregnated fibers into a composite material comprises forming the composite material at a mass loss of less than about 10%.

15. The method of claim 1 , further comprising machining the composite material.

16. The method of claim 1 , further comprising ceramifying the composite material to form a ceramic matrix composite.

17. The method of claim 16 , wherein forming the impregnated fibers into a composite material comprises curing the impregnated fibers and ceramifying the composite material at a single heat treatment at a temperature of about 1,200° C.

18. The method of claim 1 , wherein passing fibers through a preceramic resin formulation comprises passing the fibers through a preceramic resin formulation comprising the organically modified silicon dioxide preceramic polymer and a polycarbosilane preceramic polymer.

19. A preceramic resin formulation comprising an organically modified silicon dioxide preceramic polymer and at least one filler, the organically modified silicon dioxide preceramic polymer comprising quaternary coordinated oxygen to silicon atoms of the organically modified silicon dioxide preceramic polymer, and the preceramic resin formulation formulated to exhibit a viscosity of from about 200 cP at about 25° C. to about 5,000 cP at a temperature of about 25° C.

20. The preceramic resin formulation of claim 19 , wherein the at least one filler comprises first particles having an average mean diameter of less than about 1.0 μm and second particles having an average mean diameter of from about 1.5 μm to about 5 μm.

21. The preceramic resin formulation of claim 19 , wherein the at least one filler comprises silicon carbide, hafnium carbide, tantalum carbide, niobium carbide, zirconium carbide, tungsten carbide, molybdenum carbide, zirconium oxide, aluminum oxide, hafnium oxide, magnesium oxide, thorium oxide, boron nitride, hafnium nitride, tantalum nitride, zirconium nitride, titanium nitride, titanium diboride, hafnium diboride, tantalum diboride, zirconium diboride, tungsten boride, or combinations thereof.

22. The preceramic resin formulation of claim 19 , wherein the at least one filler comprises at least one of zirconium dioxide or titanium diboride.

23. The preceramic resin formulation of claim 20 , wherein the first particles of the at least one filler comprise the same material as the second particles of the at least one filler.

24. The preceramic resin formulation of claim 20 , wherein the first particles of the at least one filler comprise a different material than the second particles of the at least one filler.

25. The preceramic resin formulation of claim 19 , wherein the at least one filler comprises zirconium dioxide at an average mean diameter of from about 0.5 μm to about 0.6 μm and titanium diboride at an average mean diameter of from about 2 μm to about 5 μm.

26. The preceramic resin formulation of claim 19 , wherein the at least one filler comprises zirconium dioxide at an average mean diameter of about 0.6 μm and titanium diboride at an average mean diameter of about 3 μm.

27. The preceramic resin formulation of claim 19 , wherein the preceramic resin formulation does not comprise a surfactant.

28. The preceramic resin formulation of claim 19 , further comprising boron nitride.

29. The preceramic resin formulation of claim 19 , wherein the preceramic resin formulation further comprises a polycarbosilane preceramic polymer.

30. The preceramic resin formulation of claim 29 , wherein the polycarbosilane preceramic polymer comprises monomers having a chemical structure of

where R 1 and R 2 of each monomer is independently a hydrogen (H) group, a methyl (CH 3 ) group, a vinyl group (CH 2 ═CH) directly bonded to the sili

Assignees

• Northrop Grumman Innovation Systems Inc

Inventors

• Garcia Benjamin W C
• Nelson David R

Classifications

• B64C1/00

  Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like · CPC title

• C04B35/80

  Fibres, filaments, whiskers, platelets, or the like · CPC title

• C04B2235/3206

  Magnesium oxides or oxide-forming salts thereof · CPC title

• C04B35/62863

  Silicon carbide · CPC title

• B64C11/20

  Constructional features · CPC title