Compression/injection molding of polymer-derived fiber reinforced ceramic matrix composite materials

• US 5,738,818 A
• Filed: 08/28/1996
• Issued: 04/14/1998
• Est. Priority Date: 08/28/1996
• Status: Expired due to Term

• Current Assignee: Northrop Grumman Systems Corporation (Northrop Grumman Corporation)
• Original Assignee: Northrop Grumman Corporation
• Inventors: Atmur, Steven Donald, Strasser, Thomas Edward
• Primary Examiner(s): DERRINGTON, JAMES H
• Application Number:
  US08/704,348
• Time in Patent Office: 594 Days
• Field of Search: 264/60, 264/328.2, 264/328.12, 264/328.18, 264/624, 264/625, 264/626, 264/628, 264/640, 264/641, 264/645
• US Class Current: 264/624
• CPC Class Codes: B28B 1/24 by injection moulding injection moulding of ceramic slips B28B1/265; of tubular articles B28B21/38
• CPC Class Codes: B28B 1/52 specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cementby wrapping on to mandrels B28B1/42
• CPC Class Codes: B28B 1/522 for producing multi-layered articles B28B1/526, B28B1/527 take precedence
• CPC Class Codes: B28B 23/0006 the reinforcement consisting of aligned, non-metal reinforcing elements
• CPC Class Codes: B28B 3/025 Hot pressing, e.g. of ceramic materials
• CPC Class Codes: B29C 2045/001 Bulk moulding compounds [BMC]
• CPC Class Codes: B29C 43/003 characterised by the choice of material
• CPC Class Codes: B29C 43/02 of articles of definite length, i.e. discrete articles B29C35/0227 takes precedence
• CPC Class Codes: B29C 43/203 Making multilayered articles
• CPC Class Codes: B29C 45/0005 using fibre reinforcements
• CPC Class Codes: C04B 2235/483 Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
• CPC Class Codes: C04B 2235/5212 Organic
• CPC Class Codes: C04B 2235/5224 Alumina or aluminates
• CPC Class Codes: C04B 2235/5228 Silica and alumina, including aluminosilicates, e.g. mullite
• CPC Class Codes: C04B 2235/524 Non-oxidic, e.g. borides, carbides, silicides or nitrides
• CPC Class Codes: C04B 2235/5244 Silicon carbide
• CPC Class Codes: C04B 2235/5248 Carbon, e.g. graphite
• CPC Class Codes: C04B 2235/5252 having a specific pre-form
• CPC Class Codes: C04B 2235/526 characterised by the length of the fibers
• CPC Class Codes: C04B 2235/602 Making the green bodies or pre-forms by moulding
• CPC Class Codes: C04B 2235/6022 : Injection moulding
• CPC Class Codes: C04B 35/18 : rich in aluminium oxide
• CPC Class Codes: C04B 35/5603 : with a well-defined oxygen content, e.g. oxycarbides
• CPC Class Codes: C04B 35/571 : obtained from Si-containing polymer precursors or organosilicon monomers
• CPC Class Codes: C04B 35/6269 : Curing of mixtures
• CPC Class Codes: C04B 35/80 : Fibres, filaments, whiskers, platelets, or the like
• CPC Class Codes: F01L 3/02 : Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials

Abstract

Methods of making fiber reinforced ceramic matrix composite (FRCMC) parts by compression and injection molding. The compression molding method generally includes the initial steps of placing a quantity of bulk molding compound into a female die of a mold, and pressing a male die of the mold onto the female die so as to displace the bulk molding compound throughout a cavity formed between the female and male dies, so as to form the part. The injection molding method general includes an initial step of injecting a quantity of bulk molding compound into a cavity of a mold. In both methods, the bulk molding compound is a mixture which includes pre-ceramic resin, fibers, and, if desired, filler materials. Once the part has been formed by either method, the mold is heated at a temperature and for a time associated with the pre-ceramic resin which polymerizes the resin to form a fiber-reinforced polymer composite structure. The part is then removed from the mold, and heated a second time at a temperature and for a time associated with the polymerized resin which pyrolyzes it to form the finished FRCMC structure. These methods can also be modified to allow for the molding of heterogeneous FRCMC parts wherein different portions of the part contain different types of fiber and, if desired, different filler materials, so as to vary the characteristics exhibited by each portion thereof.

Claims

1. A method of making a fiber reinforced ceramic matrix composite (FRCMC) part comprising the steps of:

(a) injecting a quantity of bulk molding compound comprising a pre-ceramic resin and fibers into a mold having a cavity with walls which form the exterior surfaces of the FRCMC part being molded and at least one resin outlet port connecting the mold cavity to the exterior of the mold, wherein the quantity of said fibers injected corresponds to the maximum percent by volume of fibers capable of being packed within the mold cavity, and the quantity of pre-ceramic resin injected exceeds that necessary to fill the mold cavity in conjunction with the fibers and is sufficient to cause the fibers to flow with the resin and thereafter pack together within the mold cavity, and wherein excess resin exceeding that needed in conjunction with the fibers to fill the mold cavity, flows through the packed fibers and is expelled through the at least one resin outlet port;

(b) heating the mold at a temperature and for a time associated with the pre-ceramic resin which polymerizes the resin remaining in the mold cavity to form a fiber-reinforced polymer composite structure;

(c) removing the polymerized composite structure from the mold; and

(d) heating the polymerized composite structure at a temperature and for a time associated with the polymerized resin which pyrolizes it to form a FRCMC structure.

2. The method of claim 1, wherein the viscosity of the pre-ceramic resin is chosen such that it is high enough to ensure the fibers flow therewith inside the cavity of the mold, but low enough to ensure the resin readily flows through the fibers once packed into position.

3. The method of claim 2, wherein the chosen viscosity of the pre-ceramic resin is greater for longer fibers.

4. The method of claim 3, wherein said fibers are approximately the same length, said fiber length being with a range of about 0.125 inch to 12 inches, and wherein the viscosity of the pre-ceramic resin is between 5000 and 30,000 centipoise.

5. The method of claim 1, wherein each resin outlet port has a cross-sectional area small enough to substantially ensure the fibers cannot flow through the port, yet large enough to allow the flow of resin therethrough.

6. The method of claim 1 wherein the bulk molding compound further comprises a quantity of filler material which corresponds to the percent by volume of filler material desired to be dispersed throughout the FRCMC part.

7. The method of claim 6, wherein the maximum percent by volume of fibers capable of being dispersed throughout the FRCMC part is between about 15 and 50 percent dependent on the length of the fibers employed, the shape of the part being molded, and the quantity of filler material.

8. The method of claim 1, further comprising the steps of:

(e) after the completion of step (d), immersing the FRCMC part containing pores formed during step (d), into a bath of a pre-ceramic resin to fill the pores;

(f) heating the FRCMC part at a temperature and for a time associated with the resin filling said pores so as to transform it to a ceramic material;

(g) repeating steps (e) and (f) until the pore density within the FRCMC part is less than a prescribed percentage by volume.

9. The method of claim 8, wherein the resin has a water-like viscosity.

10. The method of claim 8, wherein step (f) further comprises the step of placing the FRCMC part in a vacuum environment to facilitate the filling of the pores.

11. The method of claim 8, wherein the prescribed percentage by volume of the pore density of the FRCMC part is such that the part exhibits a repeatable strength.

12. The method of claim 1 wherein said at least one resin outlet port comprises a first outlet port set and said bulk molding compound is input into the cavity of the mold through at least one sprue channel, and wherein each outlet port of said first set is disposed at a location in the cavity of the mold which is as far away from each sprue channel as possible.

13. The method of claim 12 wherein said mold comprises additional resin outlet port sets each having at least one resin outlet port, each one of the additional port sets being disposed at a different location in the cavity of the mold between the first set of ports and the at least one sprue channel.

14. The method of claim 13 wherein each of said resin outlet port sets is capable of being opened so as to allow the flow of resin therethrough, or closed so as to prevent the flow of resin therethrough.

15. The method of claim 14 wherein step (a) of claim 1 further comprises the steps of:

initially closing all the resin outlet ports associated with every outlet port set with the exception of the first set wherein each of its ports is opened;

opening the resin outlet ports of a next set of outlet ports whenever said fiber has packed into the cavity of the mold from the locations of the first set of outlet ports to a point just adjacent to the next set of outlet ports.

16. The method of claim 15, further comprising the step of closing all open ports in other sets of resin outlet ports when opening the resin outlet ports of the next set of outlet ports.

17. A method of making a fiber reinforced ceramic matrix composite (FRCMC) part comprising the steps of:

(a) injecting a quantity of bulk molding compound comprising a pre-ceramic resin and fibers into a mold having a cavity with walls which form the exterior surfaces of the FRCMC part being molded and at least one resin outlet port connecting the cavity of the mold to the exterior of the mold, wherein the quantity of said fibers injected corresponds to the maximum percent by volume of fibers capable of being packed within a first portion of the the mold cavity and the quantity of pre-ceramic resin injected exceeds that necessary to fill the mold cavity in conjunction with the fibers and is sufficient to cause the fibers to flow with the resin and thereafter pack together within the first portion of the mold cavity, and wherein excess resin exceeding that needed in conjunction with the fibers to fill the mold cavity, flows through the packed fibers and is expelled through the at least one resin outlet port;

(b) sequentially injecting at least one additional quantity of bulk molding compound into the mold, wherein each additional quantity of bulk molding compound comprises an additional amount of the pre-ceramic resin and an additional amount of fibers, wherein the quantity of each additional amount of fibers injected corresponds to the maximum percent by volume of fibers capable of being packed within a respective additional portion of the mold cavity located adjacent a previous filled portion of the mold cavity, and wherein the quantity of each additional amount of pre-ceramic resin injected exceeds that necessary to fill the mold cavity in conjunction with the fibers and is sufficient to cause the associated additional amount of fibers to flow with the resin and thereafter pack together within the corresponding additional portion of the mold cavity, and wherein excess resin exceeding that needed in conjunction with all the fibers to fill the mold cavity, flows through the packed fibers and is expelled through the at least one resin outlet port;

(b) heating the mold at a temperature and for a time associated with the pre-ceramic resin which polymerizes the resin remaining in the mold cavity to form a fiber-reinforced polymer composite structure;

(c) removing the polymerized composite structure from the mold; and

(d) heating the polymerized composite structure at a temperature and for a time associated with the polymerized resin which pyrolizes it to form a FRCMC structure.

18. The method of claim 17, wherein the viscosity of the pre-ceramic resin is chosen such that it is high enough to ensure the fibers flow therewith inside the cavity of the mold, but low enough to ensure the resin readily flows through the fibers once packed into position.

19. The method of claim 17, wherein each quantity of bulk molding compound further comprises a quantity of filler material which corresponds to the percent by volume of filler material desired within an associated portion of the FRCMC part.

20. The method of claim 17 wherein said at least one resin outlet port comprises a first outlet port set and each quantity of bulk molding compound is input into the cavity of the mold through at least one sprue channel, and wherein each outlet port of said first set is disposed at a location in the cavity of the mold which is as far away from each sprue channel as possible.

21. The method of claim 20 wherein said mold comprises additional resin outlet port sets each having at least one resin outlet port, each one of the additional port sets being disposed at a different location in the cavity of the mold between the first set of ports and the at least one sprue channel, said different locations corresponding to the end of one of said portions of the mold cavity furthest from the at least one sprue channel.

22. The method of claim 21 wherein each of said resin outlet port sets is capable of being opened so as to allow the flow of resin therethrough, or closed so as to prevent the flow of resin therethrough.

23. The method of claim 22 wherein step (a) of claim 17 further comprises the steps of:

initially closing all the resin outlet ports associated with every outlet port set with the exception of the first set wherein each of its ports is opened;

opening the resin outlet ports of a closed set of outlet ports whenever fiber has packed into the cavity of the mold from the locations of the first set of outlet ports to a point just adjacent to the closed set of outlet ports.

24. The method of claim 23, further comprising the step of closing all open ports in other sets of resin outlet ports when opening the resin outlet ports of the closed set of outlet ports.