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Title:
CASTING TOOLING
Document Type and Number:
WIPO Patent Application WO/1995/015919
Kind Code:
A1
Abstract:
The invention provides methods for producing semi-permanent casting tooling, as well as semi-permanent casting tooling apparatus. Casting tooling including a blend of high char resin and refractory powder; casting tooling prepared from a blend of sol-gel ceramic precursor and refractory powder; and a preform including a leachable core as well as methods for their production are provided. The casting tooling of the invention can be used in casting processes including die casting, permanent mold casting and pressure infiltration casting. Also provided is an investment mold casting technique compatible with a pressure infiltration process.

Inventors:
CORNIE, James, A.
Application Number:
PCT/US1994/012564
Publication Date:
June 15, 1995
Filing Date:
November 01, 1994
Export Citation:
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Assignee:
MASSACHUSETTS INSTITUTE OF TECHNOLOGY.
International Classes:
B22D17/22; B22C1/00; B22C1/22; B22C9/02; B22C9/06; B22F3/12; C04B35/01; C04B35/52; C04B35/524; C04B35/532; C04B35/622; C04B35/634; C22C47/06; (IPC1-7): C01B31/00; B22C9/02
Foreign References:
US5178673A1993-01-12
US4348343A1982-09-07
US3907950A1975-09-23
US3893928A1975-07-08
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Claims:
What is claimed is :
1. A method for preparation of casting tooling comprising: (1) providing a high char resin; (2) providing refractory powder; (3) blending said high char resin with said refractory powder to form a plastic moldable material, (4) shaping said plastic moldable material to form a green tooling body; and (5) heating said green tooling body to convert said high char resin into a carbon char to form said casting tooling.
2. The method of claim 1 wherein said high char resin is selected to form a moldable material for shaping in step (4) and having a solid content in the range of from about 0.85 to about 1.0 volume fraction after heating in step (5) .
3. The method of claim 2 wherein said high char resin is a high char resin selected from the group consisting of phenolformaldehyde, phenolic resins, petroleum pitch, coal tar, polyacrylonitrile and furfuryl alcoholderived binders.
4. The method of claim 2 wherein said refractory powder volume fraction is in the range of from about 0.45 to about 0.85, more preferably in the range of from about 0.50 to about 0.80 and most preferably in the range of from about 0.55 to about 0.75 with the remainder selected from the group consisting of refractory resins and mixtures thereof .
5. The method of claim 1 wherein step (3) further comprises mixing a refractory powder volume fraction with said high char resin to form a stiff mixture which forms a selfsupporting green tooling body characterized by high dimensional stability during step (5) of heating said green tooling body.
6. The method of claim 4 wherein said refractory powder is a refractory powder selected from the group consisting of silicon carbide, silicon nitride, titanium carbide, titanium nitride, boron carbide, mullite, alumina silicates, graphite, alumina, zirconia, yttria, silica and mixtures thereof.
7. The method of claim 4 wherein said refractory powder is further characterized by a low coefficient of thermal expansion and a high thermal conductivity.
8. The method of claim 1 wherein step (4) of shaping said plastic moldable material is accomplished using a molding technique selected from the group consisting of pressing, injection molding, compression molding, casting and ramming.
9. The method of claim 1 wherein step (5) of heating said plastic moldable material further includes heating said green tooling body to a temperature in the range of from about 800C to about 2000C, more preferably in the range of from about 850C to about 1700C and most preferably in the range of from about 900C to about 1500C.
10. The method of claim 1 wherein said casting tooling is characterized by a sufficiently high density to withstand casting pressure .
11. Casting tooling prepared according to the method of claim 1.
12. Casting tooling apparatus characterized by a high density sufficient to withstand casting pressure comprising: (1) a high char resin; and (2) a refractory powder.
13. The method of claim 12 wherein said high char resin is selected to form a shapable and moldable material and to produce a solid content in the range of from about 0.85 to about 1.0 volume fraction in the casting tooling apparatus.
14. The apparatus of claim 13 wherein said high char resin is a high char resin selected from the group consisting of phenolformaldehyde, furfuryl alcohol derived binders, phenolic resins, petroleum pitch, coal tar and polyacrylonitrile .
15. The apparatus of claim 13 wherein said refractory powder is present in a volume fraction in the range of from about 0.50 to about 0.85, more preferably in the range of from about 0.55 to about 0.80 and most preferably in the range of from about 0.55 to about 0.75.
16. The apparatus of claim 15 wherein said refractory powder is a blend of a first refractory powder characterized by a first refractory powder particle size and of a second refractory powder characterized by a second refractory powder particle size and said first refractory powder particle size is greater than said second refractory powder particle size.
17. The apparatus of claim 15 wherein said refractory powder is a refractory powder selected from the group consisting of silicon carbide, silicon nitride, titanium carbide, titanium nitride, boron carbide, mullite, alumina silicates, graphite, alumina, zirconia, yttria, silica and mixtures thereof.
18. The apparatus of claim 12 wherein said high density is in the range of from about 60% to about 95%, more preferably in the range of from about 65% to about 95% and most preferably in the range of from about 75% to about 95%.
19. A method for preparation of casting tooling comprising: (1) providing a solgel ceramic precursor; (2) providing a refractory powder; (3) blending said solgel ceramic precursor with said refractory powder to form a plastic moldable material; (4) shaping said plastic moldable material to form a green tooling body; and (5) heating said green tooling body to convert said solgel ceramic precursor into a ceramic to form said casting tooling.
20. The method of claim 19 wherein said solgel ceramic precursor is selected from the group consisting of silica, zirconia and alumina solgel precursors.
21. The method of claim 19 wherein step (4) of shaping said plastic moldable material is accomplished using a molding technique selected from the group consisting of pressing, injection molding, compression molding, casting and ramming.
22. The method of claim 19 wherein said refractory powder is selected from the group consisting of silicon carbide, silicon nitride, titanium carbide, titanium nitride, boron carbide, mullite, alumina silicates, graphite, alumina, zirconia, yttria, silica and mixtures thereof .
23. Casting tooling apparatus produced according to the method of claim 19.
24. A preform comprising: (1) a first ply including a continuous reinforcement fiber; (2) a second ply including a continuous reinforcement fiber; and (3) a leachable core positioned between said first ply and said second ply.
25. The preform of claim 24 wherein said first ply and said second ply further include a binder.
26. The preform of claim 25 wherein said continuous reinforcement fiber is a monofilament continuous reinforcement fiber selected from the group consisting of silicon carbide, boron carbide, titanium carbide, solgelderived alumina, sapphire, yttrium aluminum garnet (YAG) , yttriaalumina eutectic and boroncontaining monofilaments and mixtures thereof.
27. The preform of claim 25 wherein said continuous reinforcement fiber is a multifilament tow continuous reinforcement fiber selected from the group of multifilament tows consisting of aluminum oxide, organometallicderived silicon carbide, organometallicderived silicon nitride, pitchbased graphite, organometallicderived titanium carbide, polyacrylonitrilebased multifilament tows and mixtures thereof.
28. The preform of claim 25 wherein said binder is a binder material which can be volatilized at a temperature in the range of from about 100C to about 650C, more preferably in the range of from about 200C to about 450C and most preferably in the range of from about 250C to about 350C.
29. The preform of claim 28 wherein said binder is a polymer selected from the group consisting of acrylics, polystyrene, polyvinyl alcohol and trimethylbutanol volatile organic compounds.
30. The preform of claim 28 wherein said acrylic is an acrylic selected from the group consisting of polymethylmethacrylate, acrylic acid, 3chlorocis acrylic acid and 3 (2 furyl) trans acrylic acid.
31. The preform of claim 25 wherein said binder further includes an organic solvent which can be volatilized at a temperature in the range of from about 0C to about 200C, more preferably in the range of from about 20C to about 150C and most preferably in the range of from about 30C to about 100C.
32. The preform of claim 31 wherein said organic solvent is an organic solvent selected from the group consisting of toluene, ethanol, ethanol, acetone and ether.
33. The preform of claim 25 wherein said binder further includes a hybridizing material .
34. The preform of claim 33 wherein said hybridizing material is a ceramic powder selected from the group consisting of titanium diboride, aluminum oxide, yttrium oxide, boron nitride, silicon carbide, silicon nitride, titanium carbide, zirconium carbide, hafnium carbide, tungsten carbide, niobium carbide, boron carbide, titanium nitride, zirconium nitride, hafnium nitride and mixtures thereof .
35. The preform of claim 33 wherein said hybridizing material is a metal powder selected from the group consisting of Mo, W, Cr, Nb and Ta.
36. The preform of claim 24 wherein said leachable core is a refractory material which can withstand processing temperatures used in production of intermetallic and superalloy matrix composites and said refractory material is soluble in a solvent.
37. The preform of claim 36 wherein said solvent is an aqueous solvent . » .
38. The preform of claim 36 wherein said solvent is a molten caustic.
39. The preform of claim 36 wherein said refractory material is a refractory material selected from the group consisting of calcium oxide, silica, alumina, mullite and alumina silicates.
40. The preform of claim 24 wherein said leachable core is a continuous planar leachable core material.
41. The preform of claim 24 wherein said leachable core material consists primarily of discrete particles.
42. A method for making a preform comprising: (1) providing first and second reinforcement plys; (2) providing a leachable core; and (3) placing said leachable core between said first and second reinforcement plys to form said preform.
43. The method of claim 42 further comprising steps of providing at least two continuous reinforcement fibers and a binder and applying said binder to said at least two continuous reinforcement fibers to hold said at least two continuous reinforcement fibers together to form a monolayer and cutting a reinforcement ply from said monolayer.
44. The method of claim 43 wherein said monolayer is formed by wrapping said at least two continuous reinforcement fibers around a mandrel and doctoring said binder onto said at least two continuous reinforcement fibers.
45. A method for pressure infiltration casting comprising steps of: (1) fabricating a preform; (2) providing a molten infiltrant; (3) fabricating a preform mold; (4) disposing said preform in said preform mold; (5) evacuating said preform and said preform mold; (6) surrounding said preform with said molten infiltrant so that said molten infiltrant does not permeate said preform to isolate a vacuum in said preform; (7) infiltrating said preform with said molten infiltrant to form an infiltrated preform; (8) solidifying said infiltrated preform to form a finished casting,* and (9) removing said finished casting from said preform mold.
46. The method of claim 45 wherein step (1) of fabricating said preform further comprises providing, a continuous reinforcement fiber selected from the group consisting of silicon carbide, boron carbide, titanium carbide, solgel'derived alumina, sapphire, yttrium aluminum garnet (YAG) , yttriaalumina eutectic and boroncontaining monofilaments and aluminum oxide, organometallicderived silicon carbide, organometallicderived silicon nitride, pitchbased graphite, organometallicderived titanium carbide, polyacrylonitrilebased multifilament tows and mixtures thereof and combining said continuous reinforcement fiber with a binder.
47. The method of claim 45 wherein in step (1) of fabricating said preform, a continuous reinforcement fiber selected from the group consisting of silicon carbide, boron carbide, titanium carbide, solgelderived alumina, sapphire, yttrium aluminum garnet (YAG) , yttriaalumina eutectic and boroncontaining monofilaments and aluminum oxide monofilament, organometallicderived silicon carbide, organometallicderived silicon nitride, pitchbased graphite, organometallicderived titanium carbide, polyacrylonitrilebased multifilament tows and mixtures thereof and a particulate reinforcement selected from the group consisting of titanium diboride, aluminum oxide, yttrium oxide, boron nitride, silicon carbide, silicon nitride, titanium carbide, zirconium carbide, hafnium carbide, tungsten carbide, niobium carbide, boron carbide, titanium nitride, zirconium nitride, hafnium nitride, Mo, W, Cr, Nb, Ta and mixtures thereof are combined with a binder to form a hybrid preform.
48. The method of claim 45 further comprising steps of providing a leachable phase in said preform and removing said leachable phase by dissolving said leachable phase in a solvent to form voids.
49. The method of claim 45 wherein in step (2) of providing said molten infiltrant, said molten infiltrant is selected from the group consisting of NiAl, Ni3Al, TiAl, Albased alloys, Mgbased alloys, Cubased alloys, Znbased alloys, Nibased alloys, Febased alloys, Cobased alloys and stainless steels.
50. The method of claim 45 wherein said preform further includes a reinforcement phase and said finished casting further includes a finished casting exterior surface and further comprising a step of wrapping said preform with a flexible refractory material to protect said reinforcement phase from oxidation at said finished casting exterior surface.
51. The method of claim 45 further comprising a step of providing a wax injection mold and suspending said preform in said wax injection mold with spacers to form a gap between said preform and said wax injection mold.
52. The method of claim 51 further comprising a step of injecting wax around said preform to fill said gap between said preform and said wax injection mold with a wax layer.
53. The method of claim 52 further comprising a step of forming an investment mold around said wax layer by coating said wax layer with an investment compound.
54. The method of claim 53 wherein said preform further includes a binder and further comprising a step of heating said preform and said investment mold to remove said wax layer and said binder so that said preform is suspended by said spacers in said investment mold.
55. The method of claim 54 further comprising steps of evacuating said investment mold and said preform and applying a first pressure sufficient to cause said molten infiltrant to flow into said gap between said preform and said investment mold.
56. The method of claim 55 wherein step (7) of infiltrating said preform further comprises a step of applying a second pressure sufficient to cause said molten infiltrant to infiltrate said preform.
57. The method of claim 45 further including a step of reusing said preform mold after step (9) of removing said finished casting from said preform mold.
58. An apparatus for holding a preform during pressure infiltration casting comprising: (1) an investment material mold having an inner investment mold wall surface and an outer investment mold wall surface; (2) a channel separating said inner investment mold wall surface from said preform; and (3) a spacer positioned in said channel between said inner investment mold wall surface and said preform for suspending said preform in said investment mold.
59. The apparatus of claim 58 wherein said channel further includes a wax layer which is evaporated by heating said apparatus during pressure infiltration.
Description:
CASTING TOOLING

Background of the Invention

1. Field of the Invention

The invention relates to a method for producing tooling and to tooling apparatus for use in casting. More particularly, the invention relates to a method for producing a mold and to a mold for casting.

2. Description of the Prior Art

Casting methods require tooling such as a mold for containing the material to be cast and imparting a shape to that material . Common casting techniques include pressure infiltration casting, die casting and permanent mold casting.

Pressure infiltration casting is a process wherein a pressure differential is used to drive infiltration of a molten infiltrant into an empty mold to produce an unreinforced casting or into a mold containing a preform to produce a reinforced casting. Such a pressure differential can be established, for example, by evacuating the mold and placing the evacuated mold in a pressure vessel where a pressurized gas provides the pressure differential needed to drive the molten infiltrant into the mold. A gas-tight environment is required so that entrapment of gas pores or pockets does not create defects in the finished casting which can be provided by a mold container. Using pressure infiltration casting, it is possible to controllably cast highly loaded, continuously reinforced and discontinuously, i.e., particulate, reinforced composites to net shape and with a dimensional tolerance of ± 0.0002in with a surface finish of 4 microinches or 0.1 micron i.e., a superfinished surface like a mirror finish. Pressure infiltration casting can also be used

to produce highly detailed unreinforced castings characterized by similar dimensional accuracy and smoothness. To achieve such results, machined graphite molds are typically utilized. Alloys cast with graphite molds include aluminum, magnesium and copper alloy castings. While graphite is easily machined and takes on a highly smooth finish, the graphite material and machining are expensive. Also, a graphite mold has a limited lifetime.

In pressure infiltration casting of reinforced composites, gas entrapment within the preform must be avoided so that gas pores or pockets will not create defects in the finished casting. A vacuum is isolated in the preform during pressure infiltration to eliminate such defects caused by entrapped gas. Since any gas leak will reduce the pressure gradient for infiltration, thereby resulting in incomplete infiltration and entrapped gas porosity in the finished casting, conventional, porous investment casting compounds cannot be used in pressure infiltration processes.

Permanent mold casting is a process which is described in ASM Metals Handbook. Ninth Edition, V. 15, page 275, as "gravity die casting, a metal mold consisting of two or more parts ... repeatedly used for the production of many castings of the same form" . Die casting is a process, as also given by ASM Metals Handbook, Ninth Edition, V.15, page 286, "characterized by a source of hydraulic energy that imparts high velocity to molten metal to provide rapid filling of a metal die. The die absorbs the stresses of injection, dissipates the heat contained in the metal, and facilitates the removal of the shaped part in preparation for the next cycle. The hydraulic energy is provided by a system that permits control of actuator position, velocity, and acceleration to optimize flow and force functions on the metal as it fills the cavity and solidifies."

Steel molds are conventionally used in die casting and permanent mold casting processes. Materials die cast and permanent mold cast in steel molds include alloys of aluminum, magnesium and zinc. Machined graphite molds have a lower coefficient of thermal expansion than steel molds and produce castings characterized by higher tolerances at a lower cost than steel molds of comparable tolerance. However, graphite molds oxidize above 400C and must be coated, resulting in a shorter lifetime for the graphite molds than for comparable steel molds which typically have lifetimes of approximately 40,000 castings for die casting and up to 100,000 castings for permanent mold casting. When large numbers of parts are being cast, steel molds are, therefore, more economical than graphite molds for die casting and permanent mold casting.

When large numbers of parts are being cast by any of the already-described processes, mold properties and production become key factors determining the economics of the casting process. Thus, there exists a need for a semi-permanent mold made of a mold material conformable to the fine details of a part shape and also characterized by sufficient green strength to allow removal of the mold material from the pattern for the part shape. The mold must undergo curing and outgassing without distortion or excessive shrinkage. The cured, finished mold must be strong and shock resistant so that it can be used for many castings. Also, high mold thermal conductivity is desired to enhance the solidification rate in pressure infiltration, die casting and permanent mold casting processes. A need also exists for a gas-tight standard investment compound mold for use with a pressure infiltration process for production of reinforced composites.

Summary of the Invention

The invention provides a method for making a semi-permanent mold, as well as a semi-permanent mold apparatus which is conformable to the fine details of a part shape while being characterized by sufficient green strength to allow removal from a pattern of the part shape. The mold produced according to the invention retains dimensional stability during curing and is strong enough to be reused for numerous castings, making the casting process economically feasible. Also, the mold of the invention is usable in pressure infiltration casting of unreinforced and reinforced castings by pressure infiltration techniques.

In one aspect of the invention, a method is provided for making casting tooling by blending a high char resin and a refractory powder to form a plastic, moldable material, shaping the plastic moldable material to form a green casting tooling body and heating the green tooling body to convert the high char resin into a carbon char to result in the finished casting tooling.

According to another aspect of the invention, a casting tooling apparatus characterized by a high enough density to withstand the pressure encountered in a casting process including a high char resin and a refractory powder is provided.

In an aspect of the invention a method for preparation of casting tooling by blending a sol-gel ceramic precursor and a refractory powder to form a plastic moldable material; shaping the plastic moldable material to form a green tooling body; and heating the green tooling body to convert the sol-gel ceramic precursor into a ceramic to produce the finished casting tooling is provided.

According to other aspects of the invention, a preform including first and second plys which further include a continuous reinforcement fiber separated by a leachable core positioned between the first and second plys and a method for making such a preform are provided.

Finally, in another aspect of the invention, a pressure infiltration process which includes a step of surrounding a preform

with molten infiltrant to isolate a vacuum within the preform is also provided.

Brief Description of the Drawings

FIG. 1 is a schematic illustration of a blend of refractory powders having different particle sizes in a binder material.

FIG. 2 is a schematic illustration of the step of wrapping a continuous monofilament reinforcement in production of a leachable core preform.

FIG. 3 is a schematic illustration of the step of doctoring binder slurry onto the wrapped continuous monofilament shown in FIG. 2.

FIG. 4 is a schematic illustration in cross-section of a single ply of the continuous monofilament fiber reinforcement shown in FIG. 2 embedded in the binder applied during the doctoring step shown in FIG. 3.

FIG. 5 is a schematic illustration in cross-section of a leachable core preform including several of the plys shown in FIG. 4.

FIG. 6 is a schematic illustration of a preform.

FIG. 7 is a schematic illustration of the preform shown in FIG. 6 encased in a layer of wax.

FIG. 8 is a schematic illustration of the wax injection mold shown in FIG. 7 surrounded by ceramic investment mold material.

FIG. 9 is a schematic illustration in cross-section of the mold shown in FIG. 7 used in a pressure infiltration process before infiltration of the preform with the molten infiltrant.

FIG. 10 is a schematic illustration of the pressure infiltration process shown in FIG. 9 after infiltration of the preform with the molten infiltrant.

FIG. 11 is a detailed representation of the section of the preform in contact with the mold wall.

Detailed Description of the Invention

The invention in its several aspects provides semi-permanent casting tooling and methods for producing the casting tooling which

are less expensive than production of machined graphite or machined steel tools commonly used in permanent mold casting, die casting and pressure infiltration casting. Furthermore, the tooling provided by the invention is usable in a pressure infiltration process.

According to a method of the invention, such casting tooling can be made by blending a high char resin with a refractory powder to form a moldable plastic material; shaping the material into a green tooling body; and heating the green tooling body to convert the high char resin into a carbon char to form the finished casting tooling. The high char resin can be characterized by a char yield which as used herein in the specification and claims refers to the amount of carbon which remains after heating the resin to a temperature at which the resin decomposes.

For example, a commercially available material, Plenco 11965™ liquid resin, manufactured by Plastics Engineering Company, is an unfilled phenolic with a specific gravity of 1.175 to 1.2340 g/cc and polymerizes to a solid body with a solid content of 81% to 86% of the original material after three hours at 135C or a density of approximately lg/cc. If there were no volatiles present, the Plenco 11965 ™ resin can be said to have a char yield of 44% as compared with graphite which has a density to 2.25g/cc. Another commercially available product Plenco 05350™ is filled with graphite and has a molded density of 1.78 g/cc. Upon heating to high carbonization temperatures, the density increases to 1.788 g/cc which by comparison with graphite's density of 1.788 g/cc can be considered a char yield of 80%.

In selection of a resin, several factors must be taken into consideration. While a high char yield is desirable so that the final material produced has a volume fraction of solids of in the range of from about 0.85 to about 1.0, the material must have a workable, moldable viscosity and consistency.

Resins having char yields in the range of from about 30% to about 95%, more preferably in the range of from about 45% to about 90% and most preferably in the range of from about 60% to about 90% are suitable for use in the method of the invention. High char

resins include organic resins such as phenolformaldehyde, phenolic resins, petroleum pitch, coal tar, polyacrylonitrile and furfuryl alcohol-derived binders.

The high char resin is mixed with a refractory powder which as used herein in the specification and claims refers to a powdered material characterized by a high melting temperature, typically in excess of about 1000C such as silicon carbide, silicon nitride, titanium carbide, titanium nitride, boron carbide, mullite, alumina silicates, graphite, alumina, zirconia, yttria, silica or mixtures thereof. The refractory powder is mixed with the high char resin at a refractory powder volume fraction which is appropriate to form a stiff mixture having a consistency appropriate to form a self-supporting green tooling body which maintains high dimensional stability during heating to convert the high char resin into carbon char. The viscosity of the mixture can be adjusted as necessary for processing by addition of solvent to the high char resin or by other means as would be understood by one skilled in the art.

The volume fraction that is not filled by the packed refractory powder is filled in with high char resin, which can further include a filler such as graphite powder. When the resin is converted to a char, assuming a 60% char yield for the high char resin, for the purposes of illustration, the 0.45 volume fraction occupied by the high char resin will be filled carbon char which is 60% of the original 0.45 volume fraction of the resin. Thus, the final density of the high char resin and refractory powder after conversion of the resin to char will be 0.55 + (.60 x 0.45) = .82. In order to obtain a particular final packing density, both the volume fraction of the high char resin originally present as well as its char yield must be taken into consideration. The effective char yield of the high char resin can be increased by including a graphite filler in the high char resin before combining it with the refractory powder. Using these techniques, final packing densities approaching the 85% - 90% of conventionally available graphite tooling can be achieved.

The refractory powder can have a low coefficient of thermal expansion and a high thermal conductivity and can impart these

desirable characteristics to the tooling body. Thus, for example, producing a mold which retains high dimensional tolerances through processing and is sufficiently thermally conductive, characterized by a thermal conductivity in the range of from about 75 W/m-K to about 250 W/m-K to provide controlled solidification. It is noted for the sake of comparison that steel has a thermal conductivity in the range of from about 40-80 W/m-K. Silicon carbide, for example, has a low coefficient of thermal expansion of approximately 4xl0 "6 /K and high thermal conductivity of approximately 180 W/m-K. A refractory powder material having a coefficient of thermal expansion in the range of from about 3xlO "6 /K to about 10xlO "6 /K and a thermal conductivity in the range of from about 30W/m-K to about 300W/m-K is suitable for use in the method of the invention.

The high char resin can also be mixed with a catalyst that will cause cross-linking and setting of the polymer to create a semi-rigid body before the heating step to convert the high char resin to carbon char. For example, Plenco 11956™ resin was mixed with Plenco 11704™ catalyst, a mixture of sulphonic acid, water and phosphoric acid to catalyze setting of the resin. The resin was later converted to vitreous carbon by slow heating to 1000C. Alternatively, the high char resin can be thermally set during the early stages of the heating step.

Since, during the heating of the high char resin to convert it to carbon char, it is necessary that volatile substances such as water, carbon dioxide and hydrocarbons resulting from the decomposition of the resin and the pyrolysis to carbon be removed from the green tooling body, finely divided cellulose or wood flour can be mixed with the high char resin and refractory powder. When the cellulose or wood flour burns away during the heating process, but before the conversion of the high char resin to carbon char, it will leave behind interconnected porosity which will allow venting of volatiles from the high char resin which is undergoing conversion.

The plastic moldable material can be shaped using a molding technique such as pressing, for example, with a hydraulic press,

injection molding, compression molding, casting or by ramming the plastic moldable material around a pattern.

The green tooling body can be heated to a temperature in the range of from about 800C to about 2000C, more preferably in the range of from about 850C to about 1700C and most preferably in the range of from about 900C to about 1500C. The heating process can be carried out in a vacuum or inert atmosphere in order to prevent oxidation of the carbon. At temperatures of approximately 800C, the high char resin conversion product is predominantly glassy carbon. At higher temperatures in excess of 1200C, the carbon becomes more graphitic in nature. At temperatures of approximately 800C, the high char resin conversion product is predominantly glassy carbon. At higher temperatures in excess of 1200C, the carbon becomes more graphitic in nature. The more graphitic the char, the higher the conductivity. Hence the conductivity of tooling made from more highly graphitic carbon will increase. A more highly conductive tool will result in more rapid heat removal from the mold, hence more rapid solidification rates. This leads to greater productivity for the casting process in which the tooling is used.

The finished casting tooling is characterized by a sufficiently high density which can be in the range of from about 60% to about 95%, more preferably in the range of from about 65% to about 95% and most preferably in the range of from about 75% to about 95% to withstand the pressure encountered during the casting process, such as permanent mold casting, die casting or pressure infiltration casting in which the casting tooling can be used as a mold for casting a shaped part. As used herein, in the specification and claims, the term "percent density" refers to 100 - the void percent or, equivalently, (1 -void fraction) x 100.

The invention also provides casting tooling prepared according to the already-described method and casting tooling apparatus including a high char resin and a refractory powder wherein the high char resin and the refractory powder have the already-described characteristics. Furthermore, the refractory powder can itself be a blend of a first refractory powder characterized by a first

refractory powder particle size and a second refractory powder characterized by a second refractory powder particle size. The blend can be selected to give a desired refractory powder volume fraction as shown schematically in FIG. 1 where 2 parts by volume of -80 to +100 mesh (177-149 micron) ceramic powder 10 is mixed with one part by volume of -325 to +400 mesh (44-37 micron) ceramic powder 12 and with 1.5 parts by volume high char resin 14 to which 600 mesh (15 micron) graphite particles have been added to result in a blend having approximately 0.50 volume fraction graphite. Such blends can result in 85% to 90% dense carbonized composites.

The invention also provides a method for producing pressure infiltration tooling including steps of blending a sol-gel ceramic precursor with a refractory powder to form a moldable material; shaping the moldable material to form a green tooling body; and heating the green tooling body to convert the sol-gel ceramic precursor into a ceramic to form the finished casting tooling. The sol-gel precursor can be a precursor such as an alumina, zirconia or silica sol-gel precursor and the refractory powder can be a powder such as silicon carbide, silicon nitride, titanium carbide, titanium nitride, boron carbide, mullite, alumina silicates, graphite, alumina, zirconia, yttria, silica and mixtures thereof. The volume fractions of sol-gel ceramic precursor and of refractory powder combined can be selected to result in casting tooling having the required thermal conductivity, coefficient of thermal expansion, and density needed to fulfill the demands of the particular casting process in which the casting tooling is to be used. The heating conditions required to result in the appropriate conversion of sol-gel ceramic precursor into ceramic can be determined by one skilled in the art of sol-gel chemistry.

The plastic moldable mixture including the sol-gel precursor and refractory powder can be shaped using a molding technique such as pressing, for example, with a hydraulic press, injection molding, compression molding, casting or by ramming the plastic moldable material around a pattern.

The invention also provides a preform including first and second plys which each further include a continuous reinforcement fiber and are separated by a leachable core positioned between the plys. As used herein in the specification and the claims, a ply refers to a layer of continuous reinforcement fibers aligned at an approximately constant spacing in a plane. Since the core is dissolvable, it can be leached away after the casting process is over and before final finish machining.

The first and second plys can also include a binder mixed with the continuous reinforcement fiber. As used herein in the specification and the claims, the term continuous reinforcement fiber is used to refer to a fiber which is for the most part continuous from one end of the ply to another. While the yarn may include a few broken fibers, they are in the minority, as distinguished from discontinuous reinforcements such as short or chopped fibers, whiskers and particles. A parameter known as the average length to diameter ratio (1/d) is sometimes used to distinguish continuous reinforcements from discontinuous reinforcements. Assuming that the fibers are aligned parallel to each other, fibers having 1/d greater than 30 as defined by the shear lag equations commonly used in composite material mechanics, behave mechanically as if they were continuously reinforced. Continuous fibers include monofilament continuous reinforcement fibers such as silicon carbide, boron carbide, titanium carbide, sol-gel-derived alumina, sapphire, yttrium aluminum garnet (YAG), yttria-alumina eutectic and boron-containing monofilaments and mixtures thereof as well as multifilament tow continuous reinforcement fibers such as aluminum oxide, organometallic-derived silicon carbide, organometallic-derived silicon nitride, pitch-based graphite, organometallic-derived titanium carbide, polyacrylonitrile-based multifilament tows and mixtures thereof .

The binder can be a material which can be volatilized at a temperature in the range of from about 100C to about 650C, more preferably in the range of from about 200C to about 450C and most preferably in the range of from about 250C to about 350C and can be a

polymer such as acrylics, polystyrene, polyvinyl alcohol or tri ethylbutanol . The binder can be volatilized in a vacuum or inert atmosphere. The acrylic can be polymethylmethacrylate, acrylic acid, 3-chloro-cis acrylic acid and 3- (2 furyl) trans acrylic acid. Additionally, the binder can include an organic solvent which can be volatilized at a temperature in the range of from about OC to about 200C, more preferably in the range of from about 20C to about 150C and most preferably in the range of from about 30C to about 100C such as toluene, ethanol, methanol, acetone or ether.

A hybridizing material such as titanium diboride, aluminum oxide, yttrium oxide, boron nitride, silicon carbide, silicon nitride, titanium carbide, zirconium carbide, hafnium carbide, tungsten carbide, niobium carbide, boron carbide, titanium nitride, zirconium nitride or hafnium nitride ceramic powder or a metal powder such as Mo, W, Cr, Nb or Ta or mixtures thereof.

The leachable core component of the preform is a material which can withstand the processing temperatures used in the production of intermetallic and superalloy matrix composites and is soluble in a solvent so that it can be leached away to leave behind channels or voids in the finished cast composite part. The leachable core can be soluble in an aqueous solvent or molten caustic and can be a refractory material such as calcium oxide, silica, alumina, mullite or aluminum silicates. The leachable core material can be provided as continuous planar material or as discrete particles having round, rod-like or bar-like shapes.

A method for making a preform includes the steps of providing at least two reinforcement plys and placing a leachable core material between the two plys as shown schematically in FIGS. 2-11.

Continuous fiber reinforcement 20 is unwound from supply spool 22 and wrapped around mandrel 24 in the direction given by arrow 26 to form reinforcement mat 28 as shown in FIG. 2. Binder 30 is applied to reinforcement mat 28 using rubber doctor blade 32 as mandrel 24 rotates in the direction given by arrow 26 as shown in FIG. 3 which is a view along section 9-9 of FIG. 1. After the binder is combined with reinforcement mat 28, a reinforcement ply 40

including a monolayer composed of binder 30 and continuous fiber reinforcements 20 is produced as shown in FIG. 4. The reinforcement ply can be a single row of monofilaments or a single row of multifilament tow. If the ply includes monofilaments, a filler or hyrbridizing material is needed to keep them in place. The multifilament tows are "self-bulking" and can be kept in place simply by the wrapping process or with a clamp if the fiber volume fraction is high enough of order 0.55. The leachable cores can be rods which are laid in place and the plys of the desired thickness are laid in place and stacked to fill the spaces between the pre-assembled cores.

Resulting preform 50 includes calcium oxide leachable cores 52 surrounded by binder 30 and continuous fiber reinforcements 20. The leachable cores can also be made from other ceramic materials such as fused silica. The calcium oxide cores can be leached by water and the fused silica cores can be leached by a molten caustic such as NaOH, KOH, CaOH or blends thereof as selected to result in a desired melting point for the caustic; a hot aqueous caustic such as NaOH, KOH, CaOH or blends thereof or a hydrofluoric acid bath.

A method and apparatus for pressure infiltration casting of a reinforced composite is also provided. According to one step of the method, an evacuated preform is surrounded with molten infiltrant to isolate a vacuum in the preform. The infiltrant can be an alloy such as NiAl, Ni 3 Al, TiAl, Al-based alloys, Mg-based alloys, Cu-based alloys, Zn-based alloys, Ni-based alloys, Fe-based alloys, Co-based alloys or stainless steels.

The pressure infiltration method can be used with a preform containing continuous monofilament reinforcement fiber such as silicon carbide, boron carbide, titanium carbide, sol-gel-derived alumina, sapphire, yttrium aluminum garnet (YAG) , yttria-alumina eutectic or boron-containing monofilaments or aluminum oxide, organometallic-derived silicon carbide, organometallic-derived silicon nitride, pitch-based graphite, organometallic-derived titanium carbide, polyacrylonitrile-based multifilament tows or mixtures thereof combined with a binder. These continuous reinforcement fibers such as silicon carbide, boron carbide, titanium

carbide, sol-gel-derived alumina, sapphire, yttrium aluminum garnet (YAG), yttria-alumina eutectic and boron-containing monofilaments and aluminum oxide, organometallic-derived silicon carbide, organometallic-derived silicon nitride, pitch-based graphite, organometallic-derived titanium carbide, polyacrylonitrile-based multifilament tows and mixtures thereof can also be combined with a binder and a particulate reinforcement such a titanium diboride, aluminum oxide, yttrium oxide, boron nitride, silicon carbide, silicon nitride, titanium carbide, zirconium carbide, hafnium carbide, tungsten carbide, niobium carbide, boron carbide, titanium nitride, zirconium nitride, hafnium nitride, Mo, W, Cr, Nb, Ta or mixtures thereof to form a hybrid preform. The preform can also include a leachable phase which can be dissolved in an appropriate solvent to create voids in the finished casting usually before machining.

The method can include a step of wrapping preform 60 made up of continuous reinforcement fibers 20 and binder 30 with a flexible refractory material 62 such as alumina cloth as shown in a top view in FIG. 6. The flexible refractory material 62 will protect the reinforcement phase from oxidation at the finished casting exterior surface, if the reinforcement phase is sensitive to oxidation.

Preform 60 can be suspended in wax injection mold 70 with spacers 72 held in place by a friction fit or glued with a higher temperature wax to form a gap between wax injection mold 70 and preform 60. Spacers 72 will become embedded in wax layer 74 which is injected into wax injection mold 70 through wax injection port 71 as shown in FIG. 7. The spacers can be made from any refractory material which is able to withstand the pressure infiltration processing temperatures and which is chemically inert with respect to the infiltrant and can be metal or wettable ceramic material such as alumina, yttria, calcia, silica or nickel metal.

Preform 60 can then be removed from the wax injection mold 70 and an investment mold can be formed directly around wax layer 74 by coating wax layer 74 with investment compound layer 76 as shown in FIG. 8 to form an investment mold. The investment compound can be

any investment compound compatible with the molten infiltrant. Typical investment casting compounds include proprietary formulation with frit, silica, clays etc. Investment casting compounds can also include alumina silicates with various ratios of alumina to silica to pure alumina to pure silica, mullite and zircon sand to obtain a desired refractory property for the investment compound. The higher the alumina content, the more refractory the compound. Investment casting compound binders can include colloidal silica, ethyl silicate, sodium silicate and sol-gel alumina, zirconia and colloidal materials based on the foregoing compounds .

The investment mold configuration shown in FIG. 8 can then be heated so that the wax layer and binder are melted and evaporated away, leaving the mold suspended by spacers in the investment mold.

FIGS. 9 and 10 illustrate the use of an investment mold in a pressure infiltration process. As shown in FIG. 9, investment mold 90 is placed within evacuation vessel 92 and heated to a temperature above the melting point of infiltrant material 96. Filter 98 prevents flow of molten infiltrant material 96 from prematurely entering preform 60 before the pressurization step. However, a molten infiltrant layer 100 surrounds preform 60 in the space left behind by removal of the wax layer. The molten infiltrant can get past the filter in a number of ways. The filter can be made from a non-wettable ceramic to prevent flow of material until a slight pressure, enough to drive the material through the mold, but not into the preform is applied. The surface of the mold material can be sealed with a colloidal and vitrified alumina or alumina silicate to prevent gas passage at low pressure through the investment material .

Alternatively, a loose filter that allows passage of the molten infiltrant under gravity to flow around and surround the preform can also be provided. Such a filter would only serve to filter dross from the molten infiltrant.

The layer of molten infiltrant serves to isolate a vacuum in the preform.

FIG. 10 shows investment mold 90 in pressure vessel 110. Pressure vessel 110 is pressurized by introduction of pressurized gas

through pressurized gas inlet 112. The pressurized gas exerts a force in the direction given by arrows 114 which forces already molten infiltrant 96 through filter 98 and into evacuated preform 60. After the already-described infiltration process is complete, the mold can be lowered in the direction given by arrow 116 into chill zone 118 so that directional solidification can be conducted to solidify the molten infiltrant. All of the molds provided by the invention must be able to withstand the pressure exerted by the molten material being cast against the mold.

Region 120 where preform 60 wrapped with flexible refractory layer 62 contacts investment mold 90 after solidification as shown in detail in FIG. 11. In FIG. 11, infiltrated preform 60 is separated from molten infiltrant layer 122 by flexible refractory material 62. It is noted that the molds of the invention can be coated with a mold release compound such as colloidal graphite or boron nitride.