US3743003A - Making investment shell molds inhibited against reaction with molten reactive and refractory casting metals - Google Patents

Making investment shell molds inhibited against reaction with molten reactive and refractory casting metals Download PDF

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US3743003A
US3743003A US00149485A US3743003DA US3743003A US 3743003 A US3743003 A US 3743003A US 00149485 A US00149485 A US 00149485A US 3743003D A US3743003D A US 3743003DA US 3743003 A US3743003 A US 3743003A
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inhibitor
mold
molybdenum
tungsten
former comprises
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US00149485A
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R Brown
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Selmet Inc
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Rem Metals Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions 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
    • B22C1/165Compositions 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C3/00Selection of compositions for coating the surfaces of moulds, cores, or patterns

Definitions

  • This invention relates to methods for making investment shell molds for the high integrity, precision cast ing of reactive and refractory metals, and to the molds prepared by such methods.
  • a disposable pattern is dip coated in a liquid suspension of columbium, molybdenum, tantalum or tungsten powder mold material and a metal oxide binder.
  • the dip coated pattern is stuccoed with at least one of these metal powders, after which it is dried.
  • Additional dip coats and stucco coats of predetermined composition are applied in number sufficient to build up a finished mold of the desired composition and strength.
  • the pattern is removed and the mold fired. It then is ready to receive molten titanium or other reactive and refractory casting metals.
  • the foregoing method of making a shell mold is highly useful and has the important advantage of producing a high integrity mold of precise dimensions.
  • the highly reactive molten metal poured into the mold may react chemically with the mold material and/or the metal oxide binder to produce a defective casting.
  • a zirconium dioxide binder may be reduced by molten titanium with the production of zirconium suboxides and oxygen.
  • the latter reacts with the molten titanium, causing alpha phase stabilization and resulting in the production of a defective casting with an embrittled surface.
  • the zirconium suboxide products some of which are gases at the casting temperature, have the potential of producing porosity in the casting.
  • the desired result may be obtained by including in at least the face dip coat slurry a proportion of a tungsten or molybdenum compound which is reducible to the free metal, and thereafter firing the green mold in an atmosphere of hydrogen, thereby forming a metallic coating on the metal oxide binder and mold material of the mold face coat.
  • This provides a physical barrier against reaction of the mold face coat constituents with molten titanium or other reactive or refractory metal subsequently introduced into the mold. This, in turn, inhibits the conversion of such constituents to undesired gases and other products, which, if produced, would degrade the casting.
  • the method of the invention is applicable to the manufacturing of molds useful in the high integrity precision casting of the reactive and refractory metals including zirconium, hafnium, molybdenum, columbium, tantalum and titanium.
  • the method makes use of a pattern which may be made of any of the disposable materials customarily employed in the manufacture of investment shell molds. Thus it may be made by conventional techniques from waxes, plastics, or other materials which readily are removed from the mold after its formation.
  • Each pattern is made by injecting the selected pattern 2 material in the fluid condition into a die, permitting it to solidify, removing it from the die and, if desired, gating the resulting pattern to a central sprue to form a pattern cluster.
  • the method of the invention is included in the procedure for making investment shell molds by subjecting the pattern cluster to an investment cycle which includes the steps of dipping the cluster into an agitated slurry of the mold material, draining, stuccoing (optionally) while still wet with particulate mold material in a fluidized bed or by sprinkling, and drying to a solvent content of preferably less than 20 percent by volume.
  • the dipping, draining, stuccoing and drying sequence is repeated a desired number of times to produce a laminated investment shell mold of the desired thickness and strength.
  • the coats of mold-forming material thus applied in general are of three categories:
  • the first coat is termed the face coat. It constitutes the inner face of the mold and is in direct contact with the molten metal poured therein.
  • a single dip coatstucco coat combination normally comprises the face coat.
  • the second category of coats termed the adjacent face coats, comprise alternate dip coats and stucco coats applied in sequence on top of the face coat. There may be any desired or necessary number of such coats.
  • the third class of coats applied in making the herein described molds are those which, during use of the molds, normally do not come in direct contact with the molten casting metal, or with the vapor produced thereform. These are termed back-up coats and comprise alternate dip coats and stucco coats applied in sufficient number to add the required strength to the mold. There normally may be a total of twelve or more adjacent face and back-up coats applied to the pattern in building up a mold.
  • the disposable pattern is removed from the mold shell by a method such as melting or solvent treatment.
  • the mold is dried in an oven to remove low temperature volatiles.
  • it is cured by firing in a hydrogencontaining atmosphere at a temperature sufficiently elevated to remove high temperature volatiles, and provide adequate bonding.
  • the mold In use of the mold, it is heated and filled with molten metal by gravity, pressure or centrifugal force. After cooling, the mold is removed from the resulting casting, the casting removed from the sprue and finished in the usual manner.
  • the foreging sequence is modified by covering the particles of metal oxide binder and mold material at the mold interface with a metallic coating. This forms a barrier which serves the important function of inhibiting the above noted undesirable reactions between the molten casting metal and the mold face coat constituents when the molten metal is introduced into the mold.
  • At least the face coat of the mold is prepared by dipping the pattern in a slurry having the following general composition:
  • the method of the invention is applicable to the preparation of molds having face coats containing as primary constituents a variety of finely divided mold materials.
  • such materials may comprise finely divided oxides characterized by having high melting points and the high stability resulting from having high free energies of formation.
  • oxides are zirconium dioxide, aluminum oxide and magnesium oxide.
  • Metallic molybdenum and tungsten in the form of their finely divided powders are particularly well suited for use as primary face coat mold materials in the compositions of the present invention. This is because of their lack of a normal tendency to form castingdamaging intermediate metallic compounds with the various reactive and refractory casting metals, and their freedom from a tendency to react with such metals to form gases which might contaminate the castings.
  • Such metal powders may be used singly or admixed with each other. They may be used in the form of the pure metals, their alloys, or their unalloyed mixtures. They are employed in finely divided, graded condition, having a particle size, for example, in the range of from below 400 mesh to mesh U.S. Sieve Series, i.e. having a particle size of from 0.1 to 4000 microns.
  • the metal oxide binders employed in the face coat of the presently described systems in general comprise certain refractory metal oxides, or compounds pyrolyzable to such oxides. These are used in the liquid state, in a dissolved condition, or as solids suspended or dispersed in aqueous or other liquid media.
  • binders which are oxides of the group 3 and group 4 metals in the Mendeleevian periodic chart (as set forth on page 30 of Advanced Inorganic Chemistry by F. G. Cotton and G. Wilkinson; Interscience Publishers, 1962), which have a free energy of formation at 1000I(, greater than 69 kilocalories per gram atom of oxygen in the oxide, which melt after pyrolyzation at a temperature of more than l000l(, which bond upon pyrolyzation and which provide a high temperature bond for the mold material particles.
  • Preferred binders of this class are the oxides, or the compounds which form oxides upon pyrolysis, of zirconium, thorium, hafnium, yttrium, and gadolinium.
  • Illustrative of compounds which form such oxides upon pyrolysis are the polymeric carboxylates, such as diacetato zirconic acid (zirconium acetate); the basic oxyhalogenides; the metal-organic compounds, particularly the alkoxides; the alkoxide alcoholates; the oxide alkoxide alcoholates; the polymeric alkoxides; and the oxide alkoxides; the hydrolyzed alkoxides; the halogenated alkoxides, and the hydrolyzed halogenated alkoxides; of zirconium, thorium, hafnium, yttrium and gadolinium.
  • the foreging are converted to metal oxide binders which normally mature and cure below the sintering temperature of the mold material components of the facing and adjacent facing systems, and thus normally ideally serve the purposes of the invention.
  • binders which may be employed comprise various phosphates such as magnesium phosphate and such conventional binders as calcium aluminate and sodium silicate. All of these binders, however must meet the minimum free energy of formation requirement of at least 69 kilocalories per gram atom of contained oxygen at I000K. and the minimum melting point require- 5 ment of I00OK. after pyrolyzation.
  • the third major constituent of the mold face coat slurry is an inhibitor having the ability to inhibit the deleterious reactions which may occur between some molten reactive and refractory metals cast in the mold with the various face coat mold materials and metal oxide binders employed in making the mold.
  • the inhibiting materials useful for this purpose belong to the class of compounds which are susceptible to reduction in the hydrogen environment of the mold firing furnace to form a coating of metal on the particles of metal oxide binder and mold material.
  • This coating is not necessarily completely continuous, since gaseous products are formed during its deposition. However, any discontinuities are in the form of tiny openings which are so small as to be substantially impenetratable by the molten casting metal because of the surface tension properties of the latter.
  • the coating accordingly acts as a physical barrier which retards attack on the binder and mold material by the molten casting metal. It also acts as a close proximity heat sink.
  • the inhibitor should have a sufficiently low free energy of formation so that it may be reduced to elemental metal rapidly by hydrogen.
  • the oxides of molybdenum and tungsten including molybdenum dioxide, molybdenum trioxide, tungsten dioxide, and tungsten trioxide.
  • the acids of tungsten and molybdenum and the salts thereof include molybdic acid, tungstic acid, ammonium metatungstate, and ammonium paratungstate.
  • tungsten and molybdenum containing other metals there also may be employed double salts of tungsten and molybdenum containing other metals.
  • Such compounds are lanthanum metatungstate and yttrium metatungstate. It should be noted, however, that such double compounds are only partially reducible by hydrogen to elemental metal.
  • lanthanum metatungstate is employed as an inhibitor, the tungsten oxide component is reduced'to metallic tungsten in the desired manner. The lanthanum oxide component, however, is not thus reduced, but remains innocuously as lanthanum oxide.
  • a third class of inhibitor-formers comprises the alkoxides and halogenated alkoxides of molybdenum and tungsten. These are prepared by reacting the corresponding metal halides with an alcohol having, for example, from 1 to 5 carbon atoms.
  • Important examples for the present purposes are molybdenum ethoxide ethylate, tungsten ethoxide ethylate, molybdenum chlorethoxide ethylate, tungsten trichloro diethoxide ethylate, and tungsten trichloro dimethoxide.
  • inhibitor-formers useful for the present purpose comprise the halides and oxyhalides of molybdenum and tungsten.
  • the chlorides and oxychlorides are of significance. Examples are molybdenum pentachloride, molybdenum oxytrichloride, dimolybdenum oxyoctachloride, dimolybdenum trioxypentachloride, molybdenum dioxydichloride, molybdenum oxytetrachloride, tungsten hexachloride, tungsten dioxydichloride, and tungsten oxytetrachloride.
  • inhibitor-formers may be used singly or in combination with each other in the formulation of the face coat slurries employed in the method of the present invention.
  • Another principle constituent of the face coat slurry comprises a liquid vehicle for the aforementioned materials, i.e. the mold material, the binder, and the inhibitor-former.
  • vehicle may comprise water, or various organic solvents, especially the lower aliphatic alcohols having fewer than four carbonatoms, i.e. methyl alcohol, ethyl alcohol, and the propyl alcohols. Admixtures of water and other water soluble organic solvents also may be employed.
  • binders, inhibitorformers and suspension or dispersion vehicles of the above described systems there may be employed a suitable quantity of conventional additives such as suspension agents, green strength promoters, plasticizers, wetting agents, anti-foaming agents, deflocculants, and coating driers.
  • the relative proportions of the constituents employed in the face coat slurry are somewhat variable, depending upon particular applications.
  • the metal oxide binder normally is employed in an amount of from 0.01 to 50.0 percent by weight of the mold material slurry.
  • the tungsten-or molybdenum-forming inhibitor is employed in at least the amount required for forming the coating of inhibiting metal on the metal oxide binder particles and the face coat mold material.
  • the liquid vehicle is employed in amount sufficient to impart the desired viscosity to the dip coat slurry. Suitable viscosities lie within the broad range of 50750 centistokes at room temperature.
  • a preferred method of preparing the face coat dip slurry comprises first mixing the metaloxide binder with the selected liquid vehicle and then dissolving or suspending the metal-forming inhibitor in the resulting mixture.
  • the finely divided mold material next is mixed in, as are any supplemental materials which are to be included in the mix.
  • the resulting composition then is agitated until a slurry of uniform composition is obtained.
  • the pattern In the application of the face coat dip slurry, the pattern first is treated with a suitable solvent, as required to remove any die release agent which may be present on its surface. It then is immersed with agitation in the face coat dip slurry and rotated to insure complete coverage. After a dwell period of from 5 to 60 seconds, it is withdrawn and, typically, drained for 10 to 60 seconds.
  • the wet pattern assembly then normally is stuccoed with finely divided molybdenum or tungsten having a mesh size of about 60 to (United States Sieve Series).
  • it may be stuccoed with an oxide of a metal such as zirconium, hafnium, thorium, yttrium or gadolinium, or with a selected face coat mold material.
  • the dip coated and stuccoed pattern assembly then is air dried until the coat has a solvent content of below about 20 percent by volume. If desired, gel drying or vacuum drying techniques also may be employed supplemental to, or in lieu of, air drying.
  • the dried assembly next is treated with superimposed alternating dip coats and stucco coats of predetermined composition and number until a mold of the desired size and strength has been fabricated. Thereafter, the mold is heated to fluidize and remove the disposable pattern which thus has been invested to form the mold. In next must be oven dried and cured.
  • the mold is oven dried in either air or a nonoxidizing atmosphere at from 500K. to 650K. for 4 to 8 hours. This removes most of the low temperature volatiles.
  • the mold is placed in a furnace and treated with hydrogen gas for reduction of the inhibitor-former to metallic molybdenum or tungsten.
  • the treatment with hydrogen gas preferably is effectuated in a purging environment of the latter in order to sweep out of the vicinity of the mold water vapor which usually is formed as a product of the action between the inhibitor-former and gaseous hydrogen.
  • water vapor if permitted to remain in contact with the mold, would react with the metal interface in an undesirable manner.
  • the hydrogen gas should be employed in an amount which is at least the stoichiometric amount required for reducing the inhibitor-former. This is desirable since, at least in the case of certain inhibitor-formers, a residue of the same left at the mold interface would cause the occurrence of undesirable side reactions between the mold and the casting metal poured therein.
  • the mold is heated in the hydrogen environment at a temperature and time sufficient to reduce substantially completely the inhibitor-forming compound. In the usual case, it requires heating the mold at a temperature of from 900K. to 2500K. for a time of from 2 to 4 hours. In order to prevent mold distortion or sagging, it is desirable that the final mold curing temperature be below the melting temperature of any of the mold materials which at this stage of the process still are present in the mold.
  • the molds may be vacuum processed at high temperature in known manner.
  • the heat curing in the presence of hydrogen effects reduction of the inhibitor-former to metallic molybdenum and/or tungsten.
  • This forms a metallic barrier at the mold interface and effectively covers the particles of face coat mold material and oxide binder. It thus inhibits reaction between the mold constituents and the reactive and refractory molten metals subsequently cast therein.
  • the dip slurries were prepared by adding the inhibitor-forming components and the binder components to the slurry vehicle and agitating them until a solution or a fine dispersion was obtained. The mold material then was added and the mixing continued until a uniform mixture resulted.
  • a pattern was dipped and stuccoed alternately with the compositions until the finished mold was produced.
  • the pattern then was removed by melting or solvent treatment, after which the mold was baked at from 500 K. to 650 K. for from 4 to 8 hours to remove low temperature volatiles. Thereafter, the mold was cured in a purging atmosphere of hydrogen at 9002500K. for from 2 to 4 hours.
  • the metal thus formed covered the surfaces of the binder and mold material components of the face coat, thereby forming a barrier capable of inhibiting subsequent reaction of these mold components with molten metallic titanium, zirconium, or other reactive and refractory metals subsequently cast in the mold.
  • inhibited molds for casting reactive and refractory metals using as inhibitor-forming components of the mold face coat one or a mixture of the following materials: tungsten dioxide, tungsten trioxide, molybdenum dioxide, molybdenum trioxide, tungstic acid, molybdic acid, ammonium metatungstate, lanthanum metatungstate, molybdenum chloroethoxide ethylate, tungsten triehloro diethoxide ethylate, molybdenum pentachloride, molybdenum oxytrichloride, dimolybdenum oxyoetachloride, dimolybdenum trioxypentachloride, molybdenum dioxydichloride, molybdenum oxytetrachloride, tungsten hexachloride, tungsten dioxydichloride, and tungsten oxytetrachloride.
  • inhibitorformer comprising at least one member of the group consisting of the compounds of tungsten and molybdenum which are reducible by hydrogen to metallic tungsten and molybdenum respectivcly,
  • the hydrogen being used in at least the stoichiometric amount required to reduce the inhibitorformer to the corresponding metal and thereby coat the mold interface with a metallic coating functioning, when a molten refractory and reactive metal is cast in the mold, as a barrier layer which shields the mold constituents from the casting metal and thereby inhibits the occurrence of undesirable side reactions therebetween.
  • inhibitorformer comprises at least one member of the group consisting of the oxides of tungsten and molybdenum.
  • inhibitorformer comprises molybdenum oxide.
  • inhibitorformer comprises at least one member of the group consisting of tungstic acid, molybdic acid and the salts thereof.
  • inhibitorformer comprises molybdic acid
  • inhibitorformer comprises ammonium metatungstate.
  • inhibitorformer comprises lanthanum metatungstate.
  • inhibitorformer comprises at least one member of the group consisting of the alkoxides and halogenated alkoxides of tungsten and molybdenum.
  • inhibitorformer comprises molybdenum chloroethoxide ethylate.
  • the inhibitorformer comprises tungsten chloroethoxide ethylate.
  • inhibitorformer comprises at least one member of the group consisting of the halides and oxyhalides of tungsten and molybdenum.
  • inhibitorformer comprises tungsten oxychloride.
  • inhibitorformer comprises molybdenum chloride.
  • inhibitorformer comprises molybdenum oxychloride.

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US00149485A 1971-06-03 1971-06-03 Making investment shell molds inhibited against reaction with molten reactive and refractory casting metals Expired - Lifetime US3743003A (en)

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JP (1) JPS5219163B1 (de)
AT (1) AT328106B (de)
BE (1) BE784269A (de)
CA (1) CA972129A (de)
CH (1) CH554204A (de)
DE (1) DE2226947A1 (de)
FR (1) FR2140189B1 (de)
GB (1) GB1394872A (de)
IE (1) IE36709B1 (de)
IT (1) IT958188B (de)
NL (1) NL7207552A (de)
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3802482A (en) * 1972-03-09 1974-04-09 United Aircraft Corp Process for making directionally solidified castings
US3892579A (en) * 1973-03-22 1975-07-01 American Dental Ass Adhesive refractory protective composition for investment casting
US3933190A (en) * 1974-12-16 1976-01-20 United Technologies Corporation Method for fabricating shell molds for the production of superalloy castings
US3972367A (en) * 1975-06-11 1976-08-03 General Electric Company Process for forming a barrier layer on ceramic molds suitable for use for high temperature eutectic superalloy casting
US4031945A (en) * 1976-04-07 1977-06-28 General Electric Company Process for making ceramic molds having a metal oxide barrier for casting and directional solidification of superalloys
US4159204A (en) * 1972-02-01 1979-06-26 Dynamit Nobel Aktiengesellschaft Process for the manufacture of refractory ceramic products
US4211567A (en) * 1972-02-01 1980-07-08 Dynamit Nobel Aktiengesellschaft Process for the manufacture of refractory ceramic products
US4533394A (en) * 1982-09-30 1985-08-06 Watts Claude H Process for manufacturing shell molds
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
US6766850B2 (en) 2001-12-27 2004-07-27 Caterpillar Inc Pressure casting using a supported shell mold
US20060021732A1 (en) * 2004-07-28 2006-02-02 Kilinski Bart M Increasing stability of silica-bearing material
US20060051599A1 (en) * 2002-07-01 2006-03-09 Mahnaz Jahedi Coatings for articles used with molten metal
US20130224066A1 (en) * 2012-02-29 2013-08-29 General Electric Company Mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
CN103537620A (zh) * 2013-09-30 2014-01-29 中国航空工业集团公司北京航空材料研究院 一种钛铝基合金定向凝固熔模精密铸造模壳的制备方法
US20150258602A1 (en) * 2012-10-18 2015-09-17 Cermatco Ltd Investment Binder and Use of the Investment Binder
US9511417B2 (en) 2013-11-26 2016-12-06 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
CN111545711A (zh) * 2020-05-19 2020-08-18 中国科学院金属研究所 一种高温合金lmc定向凝固用抗热冲击陶瓷型壳的制备方法
CN114570882A (zh) * 2022-03-10 2022-06-03 西部金属材料股份有限公司 一种钨面层型壳的制备方法

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FR2407770A1 (en) * 1977-11-07 1979-06-01 Rem Metals Corp Mould for casting reactive and refractory metals - has an inert facing contg. metal (oxy)fluoride, heat sink material and binder
GB9601910D0 (en) * 1996-01-31 1996-04-03 Rolls Royce Plc A method of investment casting and a method of making an investment casting mould

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US1772490A (en) * 1926-01-13 1930-08-12 Dow Chemical Co Casting magnesium and alloys therefor
US3158912A (en) * 1962-08-09 1964-12-01 Gen Electric Controlled grain size casting method
CA868258A (en) * 1971-04-13 A. Brown Robert Investment shell molds for the high integrity precision casting of reactive and refractory metals, and methods for their manufacture

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CA868258A (en) * 1971-04-13 A. Brown Robert Investment shell molds for the high integrity precision casting of reactive and refractory metals, and methods for their manufacture
US1772490A (en) * 1926-01-13 1930-08-12 Dow Chemical Co Casting magnesium and alloys therefor
US3158912A (en) * 1962-08-09 1964-12-01 Gen Electric Controlled grain size casting method

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159204A (en) * 1972-02-01 1979-06-26 Dynamit Nobel Aktiengesellschaft Process for the manufacture of refractory ceramic products
US4211567A (en) * 1972-02-01 1980-07-08 Dynamit Nobel Aktiengesellschaft Process for the manufacture of refractory ceramic products
US3802482A (en) * 1972-03-09 1974-04-09 United Aircraft Corp Process for making directionally solidified castings
US3892579A (en) * 1973-03-22 1975-07-01 American Dental Ass Adhesive refractory protective composition for investment casting
US3933190A (en) * 1974-12-16 1976-01-20 United Technologies Corporation Method for fabricating shell molds for the production of superalloy castings
US3972367A (en) * 1975-06-11 1976-08-03 General Electric Company Process for forming a barrier layer on ceramic molds suitable for use for high temperature eutectic superalloy casting
US4031945A (en) * 1976-04-07 1977-06-28 General Electric Company Process for making ceramic molds having a metal oxide barrier for casting and directional solidification of superalloys
US4533394A (en) * 1982-09-30 1985-08-06 Watts Claude H Process for manufacturing shell molds
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
US6766850B2 (en) 2001-12-27 2004-07-27 Caterpillar Inc Pressure casting using a supported shell mold
US20040211547A1 (en) * 2001-12-27 2004-10-28 Caterpiller Inc. Pressure casting using a supported shell mold
US7032647B2 (en) 2001-12-27 2006-04-25 Caterpillar Inc. Pressure casting using a supported shell mold
US20060051599A1 (en) * 2002-07-01 2006-03-09 Mahnaz Jahedi Coatings for articles used with molten metal
US20060021732A1 (en) * 2004-07-28 2006-02-02 Kilinski Bart M Increasing stability of silica-bearing material
US7258158B2 (en) 2004-07-28 2007-08-21 Howmet Corporation Increasing stability of silica-bearing material
US20130224066A1 (en) * 2012-02-29 2013-08-29 General Electric Company Mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
CN103286256A (zh) * 2012-02-29 2013-09-11 通用电气公司 用于铸塑钛和铝化钛合金的模具和表面涂层组合物以及方法
US8932518B2 (en) * 2012-02-29 2015-01-13 General Electric Company Mold and facecoat compositions
US9802243B2 (en) 2012-02-29 2017-10-31 General Electric Company Methods for casting titanium and titanium aluminide alloys
US20150258602A1 (en) * 2012-10-18 2015-09-17 Cermatco Ltd Investment Binder and Use of the Investment Binder
CN103537620A (zh) * 2013-09-30 2014-01-29 中国航空工业集团公司北京航空材料研究院 一种钛铝基合金定向凝固熔模精密铸造模壳的制备方法
US9511417B2 (en) 2013-11-26 2016-12-06 General Electric Company Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys
CN111545711A (zh) * 2020-05-19 2020-08-18 中国科学院金属研究所 一种高温合金lmc定向凝固用抗热冲击陶瓷型壳的制备方法
CN111545711B (zh) * 2020-05-19 2022-04-05 中国科学院金属研究所 一种高温合金lmc定向凝固用抗热冲击陶瓷型壳的制备方法
CN114570882A (zh) * 2022-03-10 2022-06-03 西部金属材料股份有限公司 一种钨面层型壳的制备方法

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IE36709L (en) 1972-12-03
CH554204A (fr) 1974-09-30
BE784269A (fr) 1972-10-02
GB1394872A (en) 1975-05-21
AT328106B (de) 1976-03-10
SE388138B (sv) 1976-09-27
CA972129A (en) 1975-08-05
FR2140189A1 (de) 1973-01-12
IT958188B (it) 1973-10-20
ATA456172A (de) 1975-05-15
FR2140189B1 (de) 1977-12-16
IE36709B1 (en) 1977-02-02
NL7207552A (de) 1972-12-05
JPS5219163B1 (de) 1977-05-26
DE2226947A1 (de) 1972-12-28

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