US3321005A - Method of making shell molds for casting reactive metals - Google Patents

Method of making shell molds for casting reactive metals Download PDF

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Publication number
US3321005A
US3321005A US449294A US44929465A US3321005A US 3321005 A US3321005 A US 3321005A US 449294 A US449294 A US 449294A US 44929465 A US44929465 A US 44929465A US 3321005 A US3321005 A US 3321005A
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US
United States
Prior art keywords
mold
ceramic
metals
organic
dip coat
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Expired - Lifetime
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US449294A
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English (en)
Inventor
Nick G Lirones
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Howmet Turbine Components Corp
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Howmet Corp
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Filing date
Publication date
Application filed by Howmet Corp filed Critical Howmet Corp
Priority to US449294A priority Critical patent/US3321005A/en
Priority claimed from US481728A external-priority patent/US3296666A/en
Priority to BE679564D priority patent/BE679564A/xx
Priority to NL6605151A priority patent/NL6605151A/xx
Priority to SE05238/66A priority patent/SE346711B/xx
Priority to FR1476352D priority patent/FR1476352A/fr
Application granted granted Critical
Publication of US3321005A publication Critical patent/US3321005A/en
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
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • 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

Definitions

  • the invention will be described with reference to the preparation and use of a mold formed about a heat or otherwise disposable pattern by repeatedly wetting with a dip coat composition and stuccoing to build up a monolithic structure from which the pattern is removed to leave a corresponding mold cavity into which molten metal may be directly cast to produce a metal product having a shape corresponding to the cavity left by the removed pattern.
  • the concepts of this invention Will have application also to the mold that is formed by investment of the monolithic structure in a ceramic body for support, in accordance with conventional investment casting procedures, but it is preferred to make use of the monolithic structure without investment when suflicient strength can be embodied in the walls of the monolithic structure to enable the molten metal to be poured directly therein without support.
  • such monolithic mold structures are produced by immersion of a cluster of wax patterns into a dip coat composition formulated of an inorganic binder, such as colloidal silica, and a ceramic flour such as is formed of silica, zircon, alumina, fused quartz and the like.
  • an inorganic binder such as colloidal silica
  • a ceramic flour such as is formed of silica, zircon, alumina, fused quartz and the like.
  • a stucco such as larger particles of silica, zircon, alundum, fused quartz and the like ceramic materials
  • This procedure of wetting with the dip coat composition and stuccoing is repeated for a number of times with intermediate drying until a composite layer of the desired thickness and strength has been built up about the cluster formed of a number of the patterns of wax or other preferably heat disposable material.
  • the assembly is heated to a temperature above the melting point temperature of the wax to remove the pattern and the remaining mold, having a mold cavity corresponding in shape to the displaced pattern, is fired at an elevated temperature in the range of l5002300' F. to cure the mold.
  • molds of the type described are suitable for use in casting shaped products of steels and alloys of steels including steels alloyed with nickel, cobalt and the like, they have been found to be unsuitable for use in the casting of shaped products from such high melting point metals as the refractory metals or reactive heavy metals such as titanium, zirconium, uranium, hafnium, beryllium, or other metals of the group IV-b series.
  • One of the major difficulties stems from the reactions that take place at the elevated temperature of the molten metal between the molten metals and the silicon oxides or ceramic components making up the mold. This results not only in an imperfect casting or a casting in which the reaction which takes place at the surface produces an imperfect casting but the reactions taking place operate also to ice modify the chemistry of the cast product and to produce an unsound casting.
  • colloidal graphite is incorporated as a component in the dip coat composition to coat the individual ceramic particles with the non-reactive colloidal graphite. While some improvement is derived from the described combination of colloidal graphite with the ceramic particles of the dip coat composition, a continuous protective surface is not made available whereby undesirable reactions are still capable of taking place.
  • a mold formed of ceramic material of the types described can be used in the production of shaped products of metals of the types described and alloys thereof when the individual particles of the ceramic materials making up the mold portion immediately surrounding the mold cavity, and preferably the entire crosssection of the mold walls, are provided with a substantially continuous coating of an inert carbonaceous material formed in situ in the mold by thermal decomposition of an organic material and preferably by thermal decomposition of an organic resinous material such as a phenol aldehyde resin, cresol aldehyde resin, furfural aldehyde resin, resorcinol aldehyde resin, acrylic acid ester polymer, and the like.
  • the thermally reducible organic resinous material can be incorporated into the mold by formulation of the resinous material as a part of the dip coat composition whereby such organic resinous component will become uniformly distributed substantially throughout the cross-section of the mold wall that is formed about the disposable pattern.
  • the organic resinous component can be introduced into the mold Walls after removal of the disposable pattern by impregnation of the resulting mold with a dilute solution or dispersion of the organic resinous component in a suitable solvent or aqueous medium.
  • the resinous component will thermally break down to a tenacious carbonaceous residue of an inert form of carbon or carbonaceous material which will effectively coat the inorganic or ceramic particles in at least the portions of the mold adjacent the mold cavity. This will result in a substantially continuous covering which will protect the ceramic or inorganic materials to enable the described molten metals or alloys to be poured directly into the mold cavity without reaction with components making up the mold.
  • the organic resinous component when the organic resinous component is incorporated to form a part of the dip coat composition, the organic resinous component can be embodied in the dip coat composition in addition to the conventional ceramic binder, such as colloidal silica. Instead, the inorganic binder component can be eliminated whereby the organic resinous material will function in the dip coat composition as an interim binder for the buildup of the layers of ceramic flour and stucco.
  • the dip coat composition can be formulated to contain the organic resinous component in an amount within the range of 40% by weight and preferably in an amount within the range of 25% by weight.
  • the amount of organic resinous component is preferably increased to within the range of 10-40% by weight and preferably an amount within the range of -30% by weight of the dip coat composition.
  • the organic resinous component in a dissolved state so as to form a coating about the ceramic particles upon drying.
  • a diluent in the form of a conventional aqueous medium when the resinous component is in a water soluble or A stage.
  • the dip coat composition can be formulated with an organic solvent in which the resinous material is soluble or the organic resinous component can be incorporated as a dispersed phase in the aqueous medium to enable formulation of the dip coat composition as an aqueous system.
  • the organic resinous material When the organic resinous material is incorporated by way of impregnation of an already formed mold, it is desirable to make use of the organic resinous material in a dilute solution in an organic solvent or a dilute dispersion in an aqueous medium.
  • the amount of the organic resinous component formulated into the impregnating composition will depend somewhat on the character and the molecular weight of the resinous system. As a general rule, a satisfactory impregnating composition can be formulated with the organic resinous component present in an amount within the range of 1-80% by weight and preferably 2-10% by weight. It will be understood that when a larger amount of resinous material is required in the formed mold, the impregnation process can be repeated one or more times.
  • a cluster of wax patterns is formed in the conventional manner by attachment of the patterns to runners, also formed of wax or other heat disposable materials, and to a funnel or cup which communicates with the runners to define the opening in the mold through which the molten metal is poured for filling the mold cavity.
  • the patterns, runners and/or funnel can be formed or plastic or other heat disposable materials, or of materials which can be disposed of by chemical solution, sublimation or by mere increase to room temperature, as in the frozen mercury process.
  • the cluster should be inspected for the removal of dirt, flakes or other materials which might have adhered to the surfaces of the patterns and which, if allowed to remain, would reproduce and provide imperfections in the surfaces of the metal casting.
  • Example 1 Dip coat composition (with ceramic binder): Colloidal silica (30% grade, 1.198 specific gravity) cc 8000 Zircon (99% through 325 mesh) pounds 165 Water cc 6150 Water soluble A-stage phenol aldehyde resin pounds 30 Sodium fluoride grams 110
  • Example 2 Dip coat composition (without ceramic binder):
  • Liquid phenol formaldehyde resin (Catalin 136) 27 Isopropyl alcohol 35 Silica flour (-325 mesh) 38
  • the cleaned cluster is immersed in the slurry c0mpris ing the dip coat composition to wet all of the surfaces with the exception of the lip of the pouring spout. Instead of dipping, the surfaces can be wet with the slurry of the dip coat composition by other coating techniques, such as by flow coating, spray coating and the like.
  • a finely divided, dry stucco is sprinkled over the surfaces whereby some of the stucco will adhere to the wet coating of the dip coat composition and be retained on the surfaces of the pattern for integration with the slurry of the dip coat composition to form a composite layer therewith about the cluster.
  • the stucco can also be applied onto the wet surfaces of the cluster by means of a moving bed into which the cluster is immersed substantially completely to coat the wet surfaces of the cluster with the stucco material.
  • the stucco use can be made of alumina, zircon, silicate, fused silica, with or without resinous pretreatment, and in which the stucco is dimensioned, at least in the first few coats, to be less than 50 mesh but more than mesh.
  • the cycle of wetting with the dip coat composition and stuccoing is repeated a number of times, with intermediate drying between each cycle, until -a composite layer of the desired thickness has been built up about the walls of the cluster including the patterns and parts.
  • a mold having a wall thickness built up to about A to /2 inch usually provides strength suflicient for investment or to enable the molten metal to be poured directly into the mold for the production of shaped metal products of normal weight.
  • the buildup of walls of greater thickness can be produced for use in the molding of larger and heavy castings.
  • a wall thickness of A to /2 inch can be achieved with from five to ten cycles of dip coating, stuccoing, and intermediate drying.
  • dip coat compositions of the same formulation for all cycles thereby uniformly to distribute the organic resinous material throughout the cross-section of the mold wall, it will be sufficient if only the inner one-half of the wall cross section is formed of the dip coat composition containing the organic resinous component while the remainder of the built-up wall is formed of a conventional dip coat composition formulated with ceramic materials.
  • the composite structure is dewaxed by inverting the mold and by heating to a temperature above the melting point temperature for the wax and preferably to a temperature above 400 F. but below the temperature at which the organic resinous material will be burned out of the mold.
  • Dewaxing can be carried out by other processes such as hot sand dewaxing wherein the mold is surrounded with sand preheated to a temperature within the range of 400-800 F. or in which the hot sand is poured over the mold; steam dewaxing wherein the composite structure is housed in an autoclave or else steam at high pressure is introduced onto the mold.
  • the dewaxing step can be carried out as a separate operation in the manner described but it is preferred to combine the dewaxing step with the subsequent step of curing the mold wherein the mold, with the wax pattern or after the wax pattern has been removed by one or the other of the dewaxing processes, is introduced into a zone heated to a temperature above 800 F. and preferably to a temperature within the range of 1000- 2300 F. while the atmosphere in the zone is maintained as an inert or non-oxidizing or reducing atmosphere, as by the use of an inert gas such as argon, nitrogen, carbon dioxide and the like.
  • an inert gas such as argon, nitrogen, carbon dioxide and the like.
  • the mold is cured and the organic resinous component is thermally decomposed to a stable form of carbon or carbonaceous decomposition product which effectively coats the adjacent ceramic materials with a protective coating that blocks reaction between the ceramic and hot molten metals poured into the cavity of the mold.
  • the desired cure and thermal breakdown of the organic resinous material can usually be achieved at the there is no harm in heating for a longer period of time to insure complete stabilization of the materials making up the mold.
  • the carbonaceous decomposition product that is formed is of the type which either swells or otherwise operates to fill up interstices of the mold since the formed mold is less pervious to the penetration of the molten metal poured into the mold cavity while still providing microporous openings through which the mold can breathe thereby to block reaction between .the metal and the materials of the mold while at the same time providing a more uniform smooth surface at the interface for the production of a molded product which conforms more exactly with the original shape of the mold cavity and with less surface imperfection.
  • an acceptable product of such metals which have heretofore been incapable of being processed in ceramic molds.
  • a solution of .5% to 25% by weight furfural formaldehyde resin or a solution of .5% to 80% by Weight of a phenol or cresol formaldehyde resin in propanol is poured into the mold cavity for flow as by impregnation into the interstices of the porous mold.
  • the step of impregnation can be repeated one or more times if a higher concentration of the organic resinous component is desired in the mold walls.
  • the step of pour ing the impregnating composition into the mold is followed by removal of the material that remains and by drying before subsequent re-introduction of impregnating composition for increasing the amount of material introduced into the mold walls.
  • the dried resinous material coats the ceramic flour and stucco making up the ad jacent portions of the mold walls.
  • the mold is fired in the manner previously described for curing in an inert or non-oxidizing atmosphere to effect the thermal decomposition of the impregnating organic resinous material for reduction thereof to temperature described in from 15 to minutes but the inert carbonaceous decomposition product coating the ceramic particles of the mold and filling the interstices of the mold to block penetration of molten metal poured into the mold cavity during the subsequent. steps of metal casting.
  • both of the prevously de scribed systems may be combined to produce a mold having the organic resinous component incorporated into the walls of the mold by way of a dip coat composition and in which additional organic resinous material is incorporated, at least in the inner portions of the mold about the mold cavity, by the subsequent process of impregnation.
  • the stabilized thermal decomposition product formed of the organic resinous component is capable also of the characteristics of a binder in the cured product since a mold of the desired strength results even though no ceramic binder is present in the dip coat composition.
  • organic materials which are easily thermally decomposable to a stabilized carbon or carbonaceous reaction product can be employed as the organic component in the amounts described for the organic resinous material in the preceding examples.
  • Such other materials which can be substituted for the organic resinous materials in equivalent amounts in the foregoing examples include natural resins and gums, such as copal resin, ester gum, gum tragacanth, gum arabic, terpene resins, coumarone indene resins and the like; sugars, carbohydrates and starches such as casein, albumen, algins and the like; coal tar and petroleum resins and the like.
  • Molten metal can be poured directly :into the mold cavity for the fabrication of molded products since the mold possesses sufiicient strength and has sufficient mass integrity to enable the motlen metal to be poured directly into the mold.
  • preheating is not essential, it is desirable to preheat the mold prior to metal pouring. If the graphitized mold is to be preheated to a temperature above 800 F, it is desirable either to effect such preheat under vacuum conditions or in an inert or non-oxidizing atmosphere, as in an atmosphere of argon, nitrogen or carbon monoxide or carbon dioxide, otherwise the carbonaceous product will burn from the mold.
  • the described refractory metals, reactive heavy metals or metals of the group IV-b have a melting point far in excess of 800 B, it is desirable to achieve metal pouring by vacuum casting techniques wherein the mold is enclosed within a vacuum chamber which communicates with a melting furnace whereby a vacuum can be drawn to evacuate the chamber and the mold prior to metal poun'ng.
  • the mold and metal cast therein are preferably maintained under vacuum conditions until the poured metal has solidified or cooled to a temperature below 800 F. Thereafter, the assembly can be removed from the vacuum chamber for further processing.
  • centrifugal casting techniques can be employed in combination with metal pouring.
  • description will be made of the use of a mold embodying the features of this invention in the preparation of a cast metal product of titanium, it being understood that others of the heretofore described refractory metals, heavy reactive metals or metals of group lV-b and alloys thereof may be similarly processed.
  • the mold is housed in a vacuum chamber on the underside of a melting furnace and the molten titanium is poured under vacuum into the mold, with or without preheating the mold.
  • preheating it is desirable to preheat the mold while under vacuum conditions in which the preheat may be to a temperature up to 800 F. although preheating to higher temperatures is preferred.
  • the poured metal is allowed to cool in the vacuum chamber or under a protective inert or non-oxidizing atmosphere to a temperature below that at which oxidation of the carbonaceous material can take place before removal :of the cast metal product from the protective atmosphere of the mold.
  • the cast metal product can be removed by conventional techniques such as by impacting and shaking to disintegrate the mold and free the casting.
  • ceramic flour and ceramic stucco are intended to include flour and stucco formed of ceramic materials such as silica, fused glass, fused quartz, Zirconium silicates, ores such as beryl ores, thoria, zirconite, kyanite, mullite and sillamanite, and oxides of the types previously described including zircon and alumina.
  • organic resinous binder is selected from the group consisting of phenol aldehyde resin, cresol aldehyde resin, resorcinol aldehyde resin, and furfural aldehyde resin.
  • the organic component of the dip coat composition is selected from the group consisting of a synthetic resin, a natural resin, a gum, starch, a protein, and a carbohydrate.
  • the organic resinous component is selected from the group consisting of a phenol aldehyde resin, a cresol aldehyde resin, a resorcinol aldehyde resin, and a furfural aldehyde resin.
  • the mold is formed of a composite of a dip coat composition the solids of which consist essentially of a ceramic flour and a ceramic binder and a stucco of ceramic particles, the steps of impregnating the mold with a dilute fluid composition containing an organic compound which is easily thermally decomposable to a stable carbonaceous decomposition product, firing the impregnated mold in a non-oxidizing atmosphere to a temperature above the thermal decomposition temperature for the organic material thermally to decompose the organic material in situ in the impregnated mold.
  • the organic resinous polymer is selected from the group consisting of a phenol aldehyde resin, a cresol aldehyde resin,

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
US449294A 1965-03-22 1965-04-19 Method of making shell molds for casting reactive metals Expired - Lifetime US3321005A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US449294A US3321005A (en) 1965-04-19 1965-04-19 Method of making shell molds for casting reactive metals
BE679564D BE679564A (enrdf_load_stackoverflow) 1965-04-19 1966-04-15
NL6605151A NL6605151A (enrdf_load_stackoverflow) 1965-04-19 1966-04-18
SE05238/66A SE346711B (enrdf_load_stackoverflow) 1965-04-19 1966-04-18
FR1476352D FR1476352A (fr) 1965-03-22 1966-04-19 Procédé pour le moulage des métaux et alliages et moule obtenu selon ce procédé

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US449294A US3321005A (en) 1965-04-19 1965-04-19 Method of making shell molds for casting reactive metals
US481728A US3296666A (en) 1965-08-23 1965-08-23 Method of preparing an investment mold for use in precision casting

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BE (1) BE679564A (enrdf_load_stackoverflow)
NL (1) NL6605151A (enrdf_load_stackoverflow)
SE (1) SE346711B (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485288A (en) * 1967-03-13 1969-12-23 Precision Castparts Corp Method of making a mold for casting of refractory and reactive metals
US3498359A (en) * 1966-03-09 1970-03-03 Imp Metal Ind Kynoch Ltd Moulds for use in metal casting
US6634413B2 (en) 2001-06-11 2003-10-21 Santoku America, Inc. Centrifugal casting of nickel base superalloys in isotropic graphite molds under vacuum
US6705385B2 (en) 2001-05-23 2004-03-16 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in anisotropic pyrolytic graphite molds under vacuum
US20040060685A1 (en) * 2001-06-11 2004-04-01 Ranjan Ray Centrifugal casting of titanium alloys with improved surface quality, structural integrity and mechanical properties in isotropic graphite molds under vacuum
US6799626B2 (en) 2001-05-15 2004-10-05 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in finegrained 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
US20050016706A1 (en) * 2003-07-23 2005-01-27 Ranjan Ray 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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683296A (en) * 1951-11-17 1954-07-13 Monsanto Chemicals Method of preparing shell molds and composition therefor
US2886869A (en) * 1956-08-01 1959-05-19 John M Webb Graphite refractory molds and method of making same
US2961751A (en) * 1958-01-13 1960-11-29 Misco P C Inc Ceramic metal casting process
US2991267A (en) * 1957-04-10 1961-07-04 Morris Bean & Company Coated sand and method of making the same
US3005244A (en) * 1958-06-09 1961-10-24 Howe Sound Co Production of shell molds
US3042541A (en) * 1958-04-16 1962-07-03 Albi Mfg Company Inc Method of treating a casting mold and the treated mold

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683296A (en) * 1951-11-17 1954-07-13 Monsanto Chemicals Method of preparing shell molds and composition therefor
US2886869A (en) * 1956-08-01 1959-05-19 John M Webb Graphite refractory molds and method of making same
US2991267A (en) * 1957-04-10 1961-07-04 Morris Bean & Company Coated sand and method of making the same
US2961751A (en) * 1958-01-13 1960-11-29 Misco P C Inc Ceramic metal casting process
US3042541A (en) * 1958-04-16 1962-07-03 Albi Mfg Company Inc Method of treating a casting mold and the treated mold
US3005244A (en) * 1958-06-09 1961-10-24 Howe Sound Co Production of shell molds

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3498359A (en) * 1966-03-09 1970-03-03 Imp Metal Ind Kynoch Ltd Moulds for use in metal casting
US3485288A (en) * 1967-03-13 1969-12-23 Precision Castparts Corp Method of making a mold for casting of refractory and reactive metals
US6799626B2 (en) 2001-05-15 2004-10-05 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in finegrained isotropic graphite molds under vacuum
US6705385B2 (en) 2001-05-23 2004-03-16 Santoku America, Inc. Castings of metallic alloys with improved surface quality, structural integrity and mechanical properties fabricated in anisotropic pyrolytic graphite molds under vacuum
US6634413B2 (en) 2001-06-11 2003-10-21 Santoku America, Inc. Centrifugal casting of nickel base superalloys in isotropic graphite molds under vacuum
US20040060685A1 (en) * 2001-06-11 2004-04-01 Ranjan Ray Centrifugal casting of titanium alloys with improved surface quality, structural integrity and mechanical properties in isotropic graphite molds under vacuum
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
US6776214B2 (en) 2001-06-11 2004-08-17 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
US20050016706A1 (en) * 2003-07-23 2005-01-27 Ranjan Ray 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
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

Also Published As

Publication number Publication date
NL6605151A (enrdf_load_stackoverflow) 1966-10-20
SE346711B (enrdf_load_stackoverflow) 1972-07-17
BE679564A (enrdf_load_stackoverflow) 1966-10-17

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Effective date: 19830705