US3248763A - Ceramic, multilayer graphite mold and method of fabrication - Google Patents

Ceramic, multilayer graphite mold and method of fabrication Download PDF

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Publication number
US3248763A
US3248763A US441827A US44182765A US3248763A US 3248763 A US3248763 A US 3248763A US 441827 A US441827 A US 441827A US 44182765 A US44182765 A US 44182765A US 3248763 A US3248763 A US 3248763A
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Prior art keywords
mold
graphite
pattern
coat composition
dip coat
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Expired - Lifetime
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US441827A
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English (en)
Inventor
Nick G Lirones
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Howmet Turbine Components Corp
Howe Sound Co
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Howe Sound Co
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Priority to US441827A priority Critical patent/US3248763A/en
Application filed by Howe Sound Co filed Critical Howe Sound Co
Priority to US441814A priority patent/US3256574A/en
Priority to DE19661508664 priority patent/DE1508664B1/de
Priority to NL666603651A priority patent/NL154951B/xx
Priority to BE678129D priority patent/BE678129A/xx
Priority to GB12323/66A priority patent/GB1144130A/en
Priority to SE3761/66A priority patent/SE318679B/xx
Priority to FR54452A priority patent/FR1472478A/fr
Application granted granted Critical
Publication of US3248763A publication Critical patent/US3248763A/en
Anticipated expiration legal-status Critical
Assigned to HOWMET TURBINE COMPONENTS CORPORATION, A CORP.OF DE reassignment HOWMET TURBINE COMPONENTS CORPORATION, A CORP.OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HOWMET CORPORATON A CORP. OF DE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/165—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents in the manufacture of multilayered shell moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B22C9/04—Use of lost patterns

Definitions

  • This invention relates to the art of casting and to materials employed in the practice of same-and it relates more particularly to the preparation of molds for use in the production of shaped products of such ditficult to cast metals as titanium, zirconium, hafnium, molybdenum, tungsten, uranium, and the like metals in Group IV-B of the periodic system.
  • FIG. 1 is a flow diagram of the process embodying the practice of this invention
  • FIG. 2 is a schematic sectional view through a mold prepared in accordance with the practice of this invention.
  • FIG. 3 is a schematic sectional view through the completed mold.
  • a mold produced in accordance with the practice of this invention embodies the novel features of inertness to minimize reactions with the metals coming intocontact with the mold surface while the metal is in a fluid state and at extremely high temperature; of generation of its own non-oxidizing atmosphere for protection of the cast molten metal;' and a material which is made 'sufliciently dense in the portions about the mold cavity to inhibit flow or infiltration of molten metal into the walls of the mold Where undesirable reactions might take place to mar the surface or finish of the cast product.
  • the absorbency of the mold is reduced by treatment of the mold after cure to impregnate the mold one or more times with colloidal graphite in dilute suspension in aqueous medium. This tends to fill the spaces btween the graphite particles making up the mold walls thereby to inhibit infiltration of molten metal into the walls of the mold.
  • the desired characteristics in a stable graphite mold can be achieved, in-accordance with the practice of this invention, by modification of the process to formulate the dip coat composition to contain, in addition to the graphite flour and colloidal graphite, a significant amount of organic polymeric material which remains to form a part of the substances remaining to form the wall portion of the mold immediately adjacent the mold cavity and which, when heated to elevated temperature, as during the cure of the mold, is thermally decomposed to carbon or a stable carbonaceous material formed in situ in the mold wall.
  • the formed thermal decomposition product appears to give a greater effect in filling the pores in the mold walls thereby to increase the imperviousness of the mold to the penetration of molten metal but which continues to allow vapors to pass therethrough and which thus provides a barrier to the penetration of molten metal into the wall portions of the mold adjacent the mold cavity.
  • pattern and cluster are used interchangably to refer to a pattern 10 or cluster formed of a multiplicity of such individual patterns in which the pattern 10 comprises a material which can be removed from the mold by heat or by chemical Example 1
  • the pattern 10 is formed of conventional materials disposable by heat or chemicals, as in well known investment casting processes.
  • the pattern is molded under pressure in suitable metal molds by injection of molten wax to fill the mold and set the pattern.
  • the pattern can be formed of a thermoplastic synthetic resinous material or combinations of such plastics and wax.
  • the plurality of patterns are connected by run ners for communication with a pouring spout to form a completed cluster.
  • the cluster is to be repeatedly dipped into a slurry, it is desirable to provide a hanger rod for carrying the cluster and for suspending the cluster during the drying operations.
  • Example 2 Dip coat composition Material Percent by weight Phenol-formaldehyde (Catalin 136Catalin Corporation of America) 12.10 Isopropyl alcohol 16.0 Water 31.5
  • colloidal graphite it is preferred to make use of colloidal particles of graphite of less than 1 micron.
  • colloidal graphite it is preferred to make use of colloidal particles of graphite of less than 1 micron.
  • use can be made of a combination of such colloidal graphite with up to 50% by weight and preferably up to only 30% by weight of semi-colloidal graphite having a particle size of between 120 microns.
  • the amount of colloidal graphite in the dip coat composition may vary but it is undesirable to make use of an amount greater than 5% by weight and it is preferred to make use of an amount within the range of 0.4% to 2% by Weight.
  • the amount of graphite flour can vary between 15-45% by weight of the dip coat composition and it is preferred to make use of an amount within the range of 20-30% by weight of the dip coat composition.
  • liquid phenol formaldehyde resin instead of making use of a liquid phenol formaldehyde resin, other resinous systems which are easily reducible by thermal decomposition can be employed such as furfuryl aldehyde resins, resorcinol aldehyde resins, acrylic resins, and such natural or coal tar resins as coumarone indene, turpene resins and the like.
  • Such other synthetic resins can be employed in equivalent amounts in Example 2 with the resins being dispersed or dissolved in the dip coat composition.
  • the resinous material present in the dip coat composition in an amount within the range of 730% by weight, depending somewhat upon the amount of colloidal graphite present and it is preferred to make use of an amount of the organic decomposable material in an amount within the range of 10-20% when employed in combination with colloidal graphite binder, and from 30% when such colloidal graphite binder is absent, as will hereinafter be described.
  • the emulsifying or wetting agents and the anti-foaming agents are not essential.
  • gum tragacanth use can be made of other hydrophilic colloids, such as gums, gelatins, alginates and the like, which when present are employed in an amount within the range of 0.01% to 0.5% by weight.
  • other nonionic surface active agents may be employed such as the alkyl sulphates and the alkyl aryl sulfonates and their salts. When employed, the amount of surface active agent may range from 0.01% to 0.5 by weight of the composition.
  • the wax pattern or cluster is first inspected to remove dirt, flakes and other objects which may be adhered to the surfaces of the wax patterns and which, if allowed to remain, would impair the preparation of a good mold and lead to an imperfect casting.
  • immersed into the dip coat composition, while being The cleaned cluster is I stirred, to cover all of the surfaces of the cluster with the exception of the lip of the pouring spout.
  • the dip coat composition can be applied to achieve the desired coverage by spraying the dip coat composition onto the surfaces of the pattern.
  • the coating weight of the dip coat composition can be increased or decreased, as desired, by comparison with the amount of coating retained on the surfaces by immersion.
  • the pattern or cluster When fully coated, the pattern or cluster is suspended to drain excess dip coat composition. During drainage, the cluster can be inspected to detect air pockets which can be eliminated by addressing a stream of air onto the uncoated portions and thereafter allowing the slurry of the dip coat composition to flow onto the uncovered areas. While the cluster is being drained, it should be held in different planes designed to achieve uniform coating on all surfaces. In general, drainage should be completed within a few minutes but, in any event, in less time than would allow the coating to dry whereby the surface would not retain stucco in the desired uniform arrangement.
  • Example 3 Stuccoing- After the cluster has been allowed to drain for a short time and while the surface is still wet with the dip coat composition, the surface is stuccoed with particles of graphite having the following particle size distribution.
  • the graphite stucco will hereinafter be referred to as having a particle size of more than 150 mesh but less than 35 mesh.
  • the particles of graphite are caused to flow over the surface of the pattern until the wet surface is substantially completely covered.
  • the stucco is sprinkled onto the wet surface while constantly changing the position of the cluster substantially uniformly to cover the dip coating with a layer of stucco, while at the same time minimizing flow of the dip coat composition whereby non-uniformities might otherwisedevelop.
  • the graphite particles are rained down from above through a screening member which is constantly fed from a vibratory conveyor or else applied by means of a fluidized bed. The particles of graphite adhere to the wet coating and become partially embedded therein to become integrated with the coating formed on the wax patterns.
  • the stuccoed cluster need not be set aside for drying. However, it is preferred to slow the gellation of the dip coat so that sufficient leeway is available for the desired drainage and stucco application. Thus it is desirable to provide for an air dry for a time ranging from l025 minutes. It will be understood that the drying time may be extended indefinitely beyond the times described without harm to the structure. If desired, drying of the combined coatings can be accelerated in a humidity controlled air circulating chamber heated to a temperature up to about 100 F.
  • the particle size of the graphite stucco is not critical since the particle size of the graphite can be varied over a fairly wide range. However, for best practice of this invention, it is preferred to make use of graphite having a particle size greater than 150 mesh and less than 20 mesh.
  • the operation is repeated, that is the pattern is again wet with the dip coat composition and covered with fine particles of graphite to build up a second composite layer.
  • the coated pattern is first submerged in the prewet .composition more completely to penetrate and wet out the coated surface followed almost immediately by submersion in the dip coat composition after which the steps of drainage, stuccoing' with the fine particles of graphite, and drying are carriedv out.
  • the layers become better integrated one with the other to produce a strong and composite structure.
  • prewetting if used, dip coating, stuccoing with the dry particles of graphite and drying can be repeated several times until a mold 12 of the desired thickness and strength has been built up about the disposable pattern or cluster.
  • graphite particles of the type having a mesh size within the range of more than 150 but less than 20 are used throughout to build up the mold, it is preferred to make use of particles of graphite of larger dimension for use as the stucco after the second coat and preferably after the fifth coat.
  • graphite having the following particle size distribution may be employed:
  • Tyler screen size Percent retained on screen 8 l 10 14 20 65 35 18 65 1 Pan 1 poured.
  • the normal Wall thickness of mold can beachieved with the compositions described with from 5l0 cycles of dip coating, stuccoing, and drying.
  • Example 4 Dewaxing- After the composite mold has been produced, the disposable pattern is removed to leave a mold cavity in which the material to be molded may be cast. Pattern removal, hereinafter referred to as dewaxing, can be achieved in a number of ways:
  • hot'matrix dewaxing A new and novel concept in dewaxing graphite molds of the type described will hereinafter be referred to as hot'matrix dewaxing.
  • graphite chips preheated to an elevated temperature above the melting point temperature of the wax and preferably at least 200 F. above the melting point and more preferably to a temperature Within the range of 400-800 F.
  • the formed mold is positioned within a flask having open ends with the crucible facing downwardly in the flask.
  • the preheated or hot graphite particles are introduced into the flask in an amount to surround the mold.
  • Heat is supplied from the graphite sufficient to reduce the wax of the pattern to a state for flow gravitationally from the pouring spout of the mold while the hot graphite particles, which engulf the mold as a matrix, operate also to maintain a non-oxidizing atmosphere about the graphite mold.
  • the assembly can be heated up to a temperature for cure of the mold as to a temperature of 2300 F. or more without deterioration of the mold thereby to enable wax removal and curing to be accomplished in a single operation for complete removal of the wax pattern and cure of the mold in a fully protected atmosphere.
  • dewaxing is carried out as a step separate and apart from cure, as illustrated by the following:
  • Dewaxing can be carried out by a process referred to 'as hot sand dewaxing wherein sand heated to a temperature of 400800 F. is arranged to surround the composite for intimate contact with the outer surfaces thereof whereby rapid heat transfer is achieved into the interior to melt out the wax.
  • the hot sand can be poured about the mold or the mold can be buried in the hot sand.
  • a metal or alloy system of low melting point such as the cerro alloys, low eutectic alloys, and the like.
  • Dewaxing can be carried out with steam when the Wax patterns are formed of a material having a melting 'point range below 200 F.
  • the composite can be housed within a steam chamber or autoclave or else steam at relatively high pressure can be addressed onto the composite while it is suspended with the spout extending downwardly for drainage of the molten wax.
  • Dewaxing can be carried out in an oven heated to a temperature above the melting point temperature of the wax but below the oxidizing temperature of the graphite, or preferably at a temperature within the range of 250-800 F. in a process referred to as low temperature dewaxing, without the need to maintain a reducing atmosphere.
  • the next step in the fabrication of the mold is to cure the mold and thermally decompose the resinous or other high molecular weight organic compound embodied.
  • the mold is heated in a non-oxidizing atmosphere to a temperature within the range of 10004300 F. for
  • the described curing and thermal decomposition steps can be carried out at the same time as dewaxing when use is made of a high temperature dewaxing method, such as in (a) above. Since graphite and the organic resinous material will be consumed when heated to a temperature above 800 F. in an oxidizing atmosphere, high temperature dewaxing, cure and decomposition are carried out in a non-oxidizing atmosphere or an inert atmosphere as under vacuum or in an atmosphere of argon, nitrogen, carbon monoxide and the like. The cured mold is cooled from elevated temperature to a safe temperature below 800 F. before exposure to atmospheric conditions for continued cooling or for further processing.
  • Molten metal can be poured directly into the mold cavity of the graphite mold for the fabrication of cast products.
  • the fired graphite mold possesses sufiicient strength and has sutficient mass integrity to enable the molten metal to be poured into the mold.
  • preheating While preheating is not essential, it is desirable to preheat the mold prior to metal pouring.
  • preheated to a temperature below about 800 F. it is not necessary to preheat in a reducing or inert atmosphere, but if the graphite mold is to be preheated to a temperature above 800 F., it is essential either to preheat under vacuum conditions or in an inert or non-oxidizing atmosphere, as in an atmosphere of argon, nitrogen or carbon monoxide,
  • An important concept of this invention resides in the ability to fabricate castings of reactive and refractory metals and alloys of extremely high melting point or metals which are subject to rapid oxidation when at elevated temperature, as represented by such metals as zirconium, silicon, tantalum, titanium, and the like.
  • This technological advance stems in part from the new and novel characteristics made available from a graphite mold of the type produced by the practice of this invention coupled with the means and method by which the molding process is carried out.
  • the graphite mold embodies high temperature stability; high dimensional stability; a desirable balance of high strength and abrasion and hot metal erosion resistance, whereby the mold maintains shape during metal pouring at high temperature without so much strength as would cause tearing of the cast product responsive to differential shrinkage upon cooling; high heat conductivity for rapid cooling or controlled heat transfer for the development of best conditions in the metal poured; and the ability to maintain an inert or reducing atmosphere for the protection of the metal while in a molten or highly oxidizable state.
  • the graphite mold is transferred to the vacuum pouring furnace and the metal is poured under vacuum into the mold, with or without preheating of the mold.
  • preheating it is desirable to preheat the mold while under vacuum to insert the mold, but it is unnecessary to preheat to a temperature in excess of 800 F. although preheating to higher temperatures may be employed.
  • the poured metal is allowed to cool in the vacuum chamber or under a protective atmosphere such as argon to a temperature below that at which oxidation can take place before removal of the mold for exposure of the poured mold to the atmosphere for further cooling.
  • a protective atmosphere such as argon
  • the cast metal produced can be removed by conventional techniques of impacting and shaking to break up the mold and to free the casting and by sand blasting to remove graphite retained on the surfaces of the casting.
  • Thermal reduction of the organic resinous component of the dip coat composition depends upon the maintenance of a non-oxidizing atmosphere during the heating to elevated temperature, otherwise the organic resinous material would burn to be consumed and removed from the system.
  • the formed decomposition product operates not only to produce a mold section which is impervious to the molten metal but it also contributes to some extent the characteristics of a high temperature binder to build strength into the cured mold.
  • the concepts of this invention can also be achieved in the use of a dip coat composition in which the colloidal graphite is absent and in which its binder function is replaced by additional amounts of organic resinous or high molecular weight materials which function as an interim binder until the mold is heated to elevated temperature for thermal decomposition of the resinous or high molecular weight organic material to produce carbon or a stable form of carbonaceous material.
  • dip coat compositions formulated without colloidal graphite and which may be used as the dip coat composition instead of Example 2:
  • Example 5 Material Percent by weight Liquid phenol formaldehyde resin (Catalin 136) 27 Isopropyl alcohol 35 Graphite flour (less than 20 mesh) 38
  • Example 6 Liquid phenol formaldehyde resin (Catalin 8944) 26 Distilled Water 35 Graphite flour (less than 200 mesh) 39
  • the dried mold before firing or the fired mold can be impregnated one or more times with a dilute solution (0.5-10 percent by weight) of an organic resinous or high polymeric material of the type employed in the dip coat composition followed by firing in a non-oxidizing atmosphere to a temperature in excess of 800 F. or the dried or fired mold can be impregnated one or more times with a dilute dispersion (0.5-5 percent by weight) of colloidal graphite followed by firing at an elevated temperature in excess of 800 F. in a non-oxidizing atmosphere.
  • the steps of wetting the surfaces of the pattern with an aqueous dip coat composition consist essentially of graphite flour, colloidal graphite and an organic high molecular weight material which is thermally decomposable at elevated temperature and in a non-oxidizing atmosphere to a stable form of a material selected from the group consisting of carbon and a carbonaceous material in which the graphite flour is present in an amount within the range of 1545 percent by weight, the colloidal graphite is present in an amount up to 5 percent by weight and the organic high molecular weight material is present in an amount within the range of 7-30 percent by weight, covering the surfaces of the pattern wet with the dip coat composition with a graphite stucco, repeating the application of dip coat composition and stucco for a number of cycles with intermediate drying to build up a wall thickness about
  • anon-oxidizing atmosphere to cure the mold and thermally to reduce the organic high molecular weight material to the carbonaceous reduction reaction product in situ in the walls of the mold to produce a mold in which the wall portions about the mold cavity are relatively impervious to molten metal but which enables vapors to pass therethrough.
  • the organic high polymeric material is an organic compound selected from the group consisting of a carbohydrate, a protein and an albumen.
  • the organic high molecular weight material is a synthetic phenolaldehyde resin and is present in an amount within the range of 10 to 20 percent by weight, and in which the colloidal graphite is present in an amount within the range of 0.4 to 2.0 percent by weight and the graphite flour is present in an amount within the range of 20 to 30 percent by weight.
  • the method as claimed in claim 1 which includes the step of impregnating the cured mold with a dilute solution of an organic resinous material in which the organic resinous material is thermally decomposable at 10 elevated temperature, followed by the heating of the mold to elevated temperature thermally to decompose the resinous material.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
US441827A 1965-03-22 1965-03-22 Ceramic, multilayer graphite mold and method of fabrication Expired - Lifetime US3248763A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US441814A US3256574A (en) 1965-03-22 1965-03-22 Mold and method of fabrication
US441827A US3248763A (en) 1965-03-22 1965-03-22 Ceramic, multilayer graphite mold and method of fabrication
NL666603651A NL154951B (nl) 1965-03-22 1966-03-21 Werkwijze voor de vervaardiging van een gietvorm voor het precisiegieten van metalen, gietvorm, vervaardigd met deze werkwijze, en gietstuk, vervaardigd onder toepassing van deze gietvorm.
BE678129D BE678129A (xx) 1965-03-22 1966-03-21
DE19661508664 DE1508664B1 (de) 1965-03-22 1966-03-21 Verfahren zur herstellung von giessformen nach dem wachs ausschmelzverfahren
GB12323/66A GB1144130A (en) 1965-03-22 1966-03-21 Improvements in moulds and methods of casting
SE3761/66A SE318679B (xx) 1965-03-22 1966-03-22
FR54452A FR1472478A (fr) 1965-03-22 1966-03-22 Nouveau moule et procédé pour le moulage de précision des métaux et alliages

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US441814A US3256574A (en) 1965-03-22 1965-03-22 Mold and method of fabrication
US441827A US3248763A (en) 1965-03-22 1965-03-22 Ceramic, multilayer graphite mold and method of fabrication

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US441827A Expired - Lifetime US3248763A (en) 1965-03-22 1965-03-22 Ceramic, multilayer graphite mold and method of fabrication

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US (2) US3256574A (xx)
BE (1) BE678129A (xx)
DE (1) DE1508664B1 (xx)
GB (1) GB1144130A (xx)
NL (1) NL154951B (xx)
SE (1) SE318679B (xx)

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US3422880A (en) * 1966-10-24 1969-01-21 Rem Metals Corp Method of making investment shell molds for the high integrity precision casting of reactive and refractory metals
US4703806A (en) * 1986-07-11 1987-11-03 Howmet Turbine Components Corporation Ceramic shell mold facecoat and core coating systems for investment casting of reactive metals

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US3485288A (en) * 1967-03-13 1969-12-23 Precision Castparts Corp Method of making a mold for casting of refractory and reactive metals
CA895432A (en) * 1967-08-25 1972-03-14 Uniroyal Ltd. - Uniroyal Ltee. Method of spray forming destructible forms
US3683996A (en) * 1970-02-26 1972-08-15 Adam Dunlop Method of carbonizing refractory moulds
US3903950A (en) * 1973-12-26 1975-09-09 Howmet Corp Sandwich structure mold
US4223716A (en) * 1978-12-04 1980-09-23 Caterpillar Tractor Co. Method of making and using a ceramic shell mold
US4326326A (en) * 1980-07-09 1982-04-27 The Merion Corporation Method of making metal golf club head
GB8301616D0 (en) * 1983-01-21 1983-02-23 Steel Castings Res Ceramic shell moulds
GB2148760B (en) * 1983-10-27 1988-01-27 Bsa Foundries Limited Casting metal in a sand backed shell mould
US4862947A (en) * 1988-08-02 1989-09-05 Pcc Airfoils, Inc. Method of casting an article
ATE340665T1 (de) 2001-05-15 2006-10-15 Santoku Corp Giessen von legierungen mit isotropen graphitformwerkzeugen
CN1253275C (zh) 2001-06-11 2006-04-26 三德美国有限公司 真空下在各向同性石墨模具中离心浇铸金属合金
US6755239B2 (en) 2001-06-11 2004-06-29 Santoku America, Inc. Centrifugal casting of titanium alloys with improved surface quality, structural integrity and mechanical properties in isotropic graphite molds under vacuum
US6799627B2 (en) 2002-06-10 2004-10-05 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in titanium carbide coated graphite molds under vacuum
US6986381B2 (en) * 2003-07-23 2006-01-17 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in refractory metals and refractory metal carbides coated graphite molds under vacuum

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US3005244A (en) * 1958-06-09 1961-10-24 Howe Sound Co Production of shell molds
US3153824A (en) * 1961-12-29 1964-10-27 Martin Metals Corp Method of casting metals
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US2564308A (en) * 1950-02-14 1951-08-14 Francis A Nagel Surface treatment of molds
US2806271A (en) * 1956-04-05 1957-09-17 Misco Prec Casting Company Process of casting titanium and related metal and alloys
US2886869A (en) * 1956-08-01 1959-05-19 John M Webb Graphite refractory molds and method of making same
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US3153824A (en) * 1961-12-29 1964-10-27 Martin Metals Corp Method of casting metals
US3153826A (en) * 1962-01-10 1964-10-27 Prec Metalsmiths Inc Precision casting molds and techniques

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Publication number Priority date Publication date Assignee Title
US3422880A (en) * 1966-10-24 1969-01-21 Rem Metals Corp Method of making investment shell molds for the high integrity precision casting of reactive and refractory metals
US4703806A (en) * 1986-07-11 1987-11-03 Howmet Turbine Components Corporation Ceramic shell mold facecoat and core coating systems for investment casting of reactive metals

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DE1508664B1 (de) 1971-08-12
US3256574A (en) 1966-06-21
NL154951B (nl) 1977-11-15
BE678129A (xx) 1966-09-21
SE318679B (xx) 1969-12-15
NL6603651A (xx) 1966-09-23
GB1144130A (en) 1969-03-05

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