EP0888199B1 - Manchons, leur preparation et utilisation - Google Patents

Manchons, leur preparation et utilisation Download PDF

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Publication number
EP0888199B1
EP0888199B1 EP97916916A EP97916916A EP0888199B1 EP 0888199 B1 EP0888199 B1 EP 0888199B1 EP 97916916 A EP97916916 A EP 97916916A EP 97916916 A EP97916916 A EP 97916916A EP 0888199 B1 EP0888199 B1 EP 0888199B1
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EP
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Prior art keywords
sleeve
binder
composition
weight percent
sleeves
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EP0888199A4 (fr
EP0888199A1 (fr
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Paulo Roberto Menon
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Ashland Inc
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Ashland Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/08—Features with respect to supply of molten metal, e.g. ingates, circular gates, skim gates
    • B22C9/082—Sprues, pouring cups

Definitions

  • This invention relates to exothermic and/or insulating sleeves, their method of preparation, and their use.
  • the sleeves are prepared by shaping a sleeve mix comprising (1) a sleeve composition capable of providing a sleeve, and (2) a chemically reactive binder.
  • the sleeves are cured in the presence of a catalyst by the cold-box curing process.
  • the invention also relates to a process for casting metal parts using a casting assembly where the sleeves are a component of the casting assembly.
  • a casting assembly consists of a pouring cup, a gating system (including downsprues, choke, and runner), risers, sleeves, molds, cores, and other components.
  • a gating system including downsprues, choke, and runner
  • risers sleeves
  • molds cores
  • other components such as downsprues, choke, and runner
  • the molds and/or cores used in the casting assembly are made of sand or other foundry aggregate and a binder, often by the no-bake or cold-box process.
  • the foundry aggregate is mixed with a chemical binder and typically cured in the presence of a liquid or vaporous catalyst after it is shaped.
  • Typical aggregates used in making molds and/or cores are aggregates having high densities and high thermal conductivity such as are silica sand, olivine, quartz, zircon sand, and magnesium silicate sands.
  • the amount of binder used for producing molds and/or cores from these aggregates on a commercial level is typically from 1.0 to 2.25 weight percent based upon the weight and type of the aggregate.
  • the density of a foundry mix is typically from 1.2 to 1.8 g/cc while the thermal conductivity of such aggregates typically ranges from 0.8 to 1.0 W/m.K.
  • the resulting molds and/or cores are not exothermic since they do not liberate heat. Although molds and cores have insulating properties, they are not very effective as insulators. In fact, molds and cores typically absorb heat.
  • Risers or feeders are reservoirs which contain excess molten metal which is needed to compensate for contractions or voids of metal which occur during the casting process.
  • Metal from the riser fills such voids in the casting when metal from the casting contracts.
  • Sleeves are used to surround or encapsulate the riser and other parts of the casting assembly in order to keep the molten metal in the riser hot and maintain it in the liquid state.
  • the temperature of the molten metal and the amount of time that the metal in the riser remains molten is a function of the sleeve composition and the thickness of the sleeve wall, among other factors.
  • sleeves In order to serve their function, sleeves must have exothermic and/or insulating properties.
  • the exothermic and insulating thermal properties of the sleeve are different in kind and/or degree than the thermal properties of the mold assembly into which they are inserted.
  • Predominately exothermic sleeves operate by liberating heat which satisfies some or all of the specific heat requirements of the riser and limits the temperature loss of the molten metal in the riser, thereby keeping the metal hotter and liquid longer.
  • Insulating sleeves maintain the molten metal in the riser by insulating it from the surrounding mold assembly.
  • Foundry molds and cores do not have the thermal properties which enable them to serve the functions of a sleeve. They are not exothermic, are not effective enough as insulators, and absorb too much heat to keep the molten metal hot and liquid. Compositions used in foundry molds and cores are not useful for making sleeves because they do not have the required thermal properties and density.
  • Typical materials used to make sleeves are aluminum, oxidizing agents, fibers, fillers and refractory materials, particularly alumina, aluminosilicate, and aluminosilicate in the form of hollow aluminosilicate spheres.
  • the type and amount of materials in the sleeve mix depends upon the properties of the sleeves which are to be made. Typical densities of sleeve compositions range from 0.4 g/ml to 0.8 g/ml.
  • the thermal conductivity for aluminum at room temperature is typically greater than 200 W/m.K while the thermal conductivity for hollow aluminosilicate microspheres at room temperature ranges from 0.05 W/m.K to 0.5 W/m.K.
  • all sleeves are required to have insulating properties, or combined insulating and exothermic properties in order to minimize heat loss and to maintain the metal in a liquid state for as long a time as possible.
  • Ramming and blowing are basically methods of compacting a sleeve composition and binder into a sleeve shape.
  • Ramming consists of packing a sleeve mix (sleeve composition and binder) into a sleeve pattern made of wood, plastic, and/or metal.
  • Vacuuming consists of applying a vacuum to an aqueous slurry of a refractory and/or fibers and suctioning off excess water to form a sleeve.
  • the sleeves formed are oven-dried to remove contained water and cure the sleeve. If the contained water is not removed, it may vaporize when it comes into contact with the hot metal and result in a safety hazard. In none of these processes is the shaped sleeve chemically cured with a liquid or vaporous catalyst.
  • compositions are modified, in some cases, by the partial or complete replacement of the fibers with hollow aluminosilicate microspheres. See PCT publication WO 94/23865. This procedure makes it possible to vary the insulating properties of the sleeves and reduces or eliminates the use of fibers which can create health and safety problems to workers making the sleeves and using the sleeves in the casting process.
  • One of the problems with sleeves is that the external dimensions of the sleeves are not accurate. As a result, the external contour of the sleeves does not coincide in its dimensions with the internal cavity of the mold where the sleeve is to be inserted. In order to compensate for the poor dimensional accuracy, it is often necessary to oversize the cavity in the mold where the sleeve is to be inserted, or form or place "crush ribs" in the mold assembly which erode or deform when the sleeves are inserted into the riser cavity to provide a means of locking the sleeve in place. Alternatively, the sleeves are placed in position on the casting pattern and the mold is made around the sleeves, thus avoiding problems with sleeves that are not dimensionally accurate.
  • sleeves may lack the required thermal properties needed to maintain the molten metal in the riser reservoir in a hot and liquid state. The result is that the casting experiences shrinkage which results in casting defects. These casting defects are most likely to be scrapped which results in wasted time and metal.
  • Runners, sprues, and other components of the casting assembly also can use insulating and exothermic sleeves as coverings to maintain the temperature of the molten metal which comes into contact with them.
  • US-A-4,240,496 discloses a shaped, refractory, heat-insulting article for use in a metallurgical vessel comprising particular de-fibred bagasse or the like, a particulate refractory material and a binder.
  • the binder may be organic e.g. starch, a resin such as a urea-formaldehyde or phenol-formaldehyde resin or it may be inorganic e.g. bentonite or a silicate such as sodium silicate. Exothermically reacting materials may be included in the ingredients of the articles.
  • the articles may be in the form of sleeves. If sodium silicate is used as binder this can be made to set by the action of carbon dioxide.
  • GB-A-922,505 relates to a process for preparing feeder heads and sleeves.
  • the process comprises mixing an exothermic material, such as aluminum, with particulate vermiculite and silica.
  • the resulting sleeve composition is formed into the desired shape and exposed to carbon dioxide.
  • This invention relates to exothermic and/or insulating sleeves according to claim 1, a cold-box process for making the sleeves according to claim 19, the use of the sleeves in making metal castings according to claim 20 and a sleeve mix according to claim 21.
  • Preferred embodiments of the invention are the subject-matter of the dependent claims.
  • the sleeve mix is first shaped and then contacted with a vaporous curing catalyst.
  • the components of the cold-box sleeve mixes can be uniformly mixed so that the mixture maintains its consistency, resulting in a sleeve where the properties are uniform throughout.
  • the cold-box process results in chemically cured sleeves.
  • the process results in the higher production of sleeves per unit of time when compared to the processes known in the prior art. Additionally, there is less risk to the health and safety of workers who come into contact with the raw materials and sleeves because they are not exposed to any fibers which may cause breathing problems when ingested for prolonged periods of time.
  • the invention also relates to the sleeves produced by this process.
  • the sleeves prepared by the process are dimensionally accurate. This allows for easy insertion of the sleeve into the mold.
  • the riser sleeves can be inserted into the mold assembly by automatic methods, thereby further improving the productivity of the molding process. Since the density and thickness of the sleeve are more consistent and dimensionally accurate, the sleeves do not have to be oversized, nor is it necessary to use "crush ribs" or molds with ribs to keep the sleeve in place. Moreover, because the sleeves are sufficiently thermally stable, the castings made with casting assemblies using the sleeves do not contain shrinkage defects. This results in less scrap and greater productivity.
  • the invention also relates to the casting of ferrous and non ferrous metal parts in a casting assembly of which the sleeves are a part, and to the parts made by this casting process.
  • the casting made using these sleeves results in less waste because the sleeves enable the molten metal in the reservoir of the sleeve riser to be reduced compared to the molten metal contained in the reservoir of a sand riser cavity. Consequently, there is better utilization of the metal in the riser and this allows for additional castings to be made from the same amount of molten metal.
  • Figure 1 shows a casting assembly with two riser sleeves (side riser sleeve and top riser sleeve) inserted into the mold assembly of the casting assembly.
  • Figure 2 graphically illustrates the effect of using a sleeve to keep the molten metal hot and liquid.
  • Figure 3 shows a diagram representing a casting where shrinkage of the casting has occurred due to the inadequate thermal properties of the sleeve used. This casting is defective and will be scrapped as waste.
  • Figure 4 is a diagram showing a casting where there has been localized shrinkage of the metal riser, but no shrinkage of the casting. This localized shrinkage does not result in casting defects and waste.
  • Figure 1 shows a simple casting assembly comprising pouring cup 1 , sprue 2 , runner 3 , sleeve for side riser 4 , side riser 5 , sleeve for top riser 6 , top riser 7 , and 8 mold and/or core assembly.
  • Molten metal is poured into the pouring cup 1 where it flows through the sprue 2 to the runner 3 and other parts of the gating system, ultimately to the 8 mold and core assembly.
  • the risers 5, 7 are reservoirs for excess molten metal which is available when the casting cools, contracts and draws molten metal from the risers.
  • the sleeves 4, 6 which are inserted into the mold and/or core assembly 8 , surround the risers 5, 7 , and keep the molten metal in the riser reservoir from cooling too rapidly.
  • Figure 2 graphically illustrates the beneficial effect of using a sleeve to keep the molten metal hot and liquid.
  • Figure 3 illustrates a casting 3 where there is shrinkage 2 of the metal of the riser 1 and the metal of the casting 3 . This casting is defective and will be scrapped as waste.
  • Figure 4 illustrates a casting 3 where there is shrinkage 2 of the metal of the riser 1 , but there is no shrinkage of the metal in the casting 3 . This casting is not defective and can be used.
  • the sleeve mixes used in the subject process contain (1) a sleeve composition, and (2) an effective amount of chemically reactive binder.
  • the sleeve mix is shaped and cured by contacting the sleeve with an effective amount of a curing catalyst.
  • the sleeve composition contains exothermic and/or insulating materials, typically inorganic.
  • the exothermic and/or insulating materials typically are aluminum-containing materials, preferably selected from the group consisting of aluminum metal, aluminosilicate, alumina, and mixtures thereof, most preferably where the aluminosilicate is in the form of hollow microspheres.
  • the exothermic material is an oxidizable metal and an oxidizing agent capable of generating an exothermic reaction at the temperature where the metal can be poured.
  • the oxidizable metal typically is aluminum, although magnesium and similar metals can also be used.
  • the insulating material is typically alumina or aluminosilicate, preferably aluminosilicate in the form of hollow microspheres.
  • the oxidizing agent used for the exothermic sleeve includes iron oxide, maganese oxide, nitrate, potassium permanganate, etc. Oxides do not need to be present at stoichiometric levels to satisfy the metal aluminum fuel component since the riser sleeves and molds in which they are contained are permeable. Thus oxygen from the oxidizing agents is supplemented by atmospheric oxygen when the aluminum fuel is burned.
  • the weight ratio of aluminum to oxidizing agent is from about 10:1 to about 2:1, preferably about 5:1 to about 4:1.
  • the thermal properties of the exothermic sleeve is enhanced by the heat generated which reduces the temperature loss of the molten metal in the riser, thereby keeping it hotter and liquid longer.
  • the exotherm results from the reaction of aluminum metal which has a thermal conductivity greater than 150 W/m.K at room temperature, more typically greater than 200 W/m.K. A mold and/or core does not exhibit exothermic properties.
  • the insulating properties of the sleeve are preferably provided by hollow aluminosilicate microspheres, including aluminosilicate zeeospheres.
  • the sleeves made with aluminosilicate hollow microspheres have low densities, low thermal conductivities, and excellent insulating properties.
  • the thermal conductivity of the hollow aluminosilicate microspheres ranges from about 0.05 W/m.K to about 0.6 W/m.K at room temperature, more typically from about 0.1 W/m.K to about 0.5 W/m.K.
  • the insulating and exothermic properties of the sleeve can be varied, but have thermal properties which are different in degree and/or kind than the mold assembly into which they will be inserted.
  • the amount of aluminum in the sleeve will range from 0 weight percent to 50 weight percent, typically 5 weight percent to 40 weight percent, based upon the weight of the sleeve composition.
  • the amount of hollow aluminosilicate microspheres, in the sleeve will range from 0 weight percent to 100 weight percent, typically 40 weight percent to 90 weight percent, based upon the weight of the sleeve composition. Since in most cases, both insulating and exothermic properties are needed in the sleeves, both aluminum metal and hollow aluminosilicate microspheres will be used in the sleeve. In sleeves where both insulating and exothermic properties are needed, the weight ratio of aluminum metal to hollow aluminosilicate microspheres is typically from about 1:5 to about 1:1, preferably from about 1:1 to about 1:1.5.
  • the hollow aluminosilicate microspheres typically have a particle size of about 3 mm. with any wall thickness. Preferred are hollow aluminosilicate microspheres having an average diameter less than 1 mm and a wall thickness of approximately 10% of the particle size. It is believed that hollow microspheres made of material other than aluminosilicate, having insulating properties, can also be used to replace or used in combination with the hollow aluminosilicate microspheres.
  • the weight percent of alumina to silica (as SiO 2 ) in the hollow aluminosilicate microspheres can vary over wide ranges depending on the application, for instance from 25:75 to 75:25, typically 33:67 to 50:50, where said weight percent is based upon the total weight of the hollow microspheres. It is known from the literature that hollow aluminosilicate microspheres having a higher alumina content are better for making sleeves used in pouring metals such as iron and steel which have casting temperatures of 1300 °C to 1700 °C because hollow aluminosilicate microspheres having more alumina have higher melting points. Thus sleeves made with these hollow aluminosilicate microspheres will not degrade as easily at higher temperatures.
  • Refractories although not necessarily preferred in terms of performance because of their higher densities and high thermal conductivities, may be used in the sleeve composition to impart higher melting points to the sleeve mixture so the sleeve will not degrade when it comes into contact with the molten metal during the casting process.
  • refractories include silica, magnesia, alumina, olivine, chromite, aluminosilicate, and silicon carbide among others. These refractories are preferably used in amounts less than 50 weight percent based upon the weight of the sleeve composition, more preferably less than 25 weight percent based upon the weight of the sleeve composition.
  • alumina is used as a refractory, it is used in amounts of less than 50% weight percent based upon the weight of the sleeve composition, more preferably less than 10% weight percent based upon the weight of the sleeve composition.
  • the density of the sleeve composition typically ranges from about 0.1 g/cc to about 0.9 g/cc, more typically from about 0.2 g/cc to about 0.8 g/cc.
  • the density of the sleeve composition typically ranges from about 0.3 g/cc to about 0.9 g/cc, more typically from about 0.5 g/cc to about 0.8 g/cc.
  • the density of the sleeve composition typically ranges from about 0.1 g/cc to about 0.7 g/cc, more typically from about 0,3 g/cc to about 0.6 g/cc.
  • the sleeve composition may contain different fillers and additives, such as cryolite (Na 3 AlF 6 ), potassium aluminum tetrafluoride, potassium aluminum hexafluoride.
  • cryolite Na 3 AlF 6
  • potassium aluminum tetrafluoride potassium aluminum hexafluoride
  • binders that are mixed with the sleeve composition to form the sleeve mix are well know in the art. Any cold-box binder, which will sufficiently hold the sleeve mix together in the shape of a sleeve and polymerize in the presence of a curing catalyst, will work.
  • binders are phenolic resins, phenolic urethane binders, furan binders, alkaline phenolic resole binders, and epoxy-acrylic binders among others.
  • Particularly preferred are epoxy-acrylic and phenolic urethane binders known as EXACTCASTTM cold-box binders sold by Ashland Chemical Company. The phenolic urethane binders are described in U.S.
  • Patents 3,485,497 and 3,409,579 which are hereby incorporated into this disclosure by reference. These binders are based on a two part system, one part being a phenolic resin component and the other part being a polyisocyanate component.
  • the epoxy-acrylic binders cured with sulfur dioxide in the presence of an oxidizing agent are described in U.S. Patent 4,526,219 which is hereby incorporated into this disclosure by reference.
  • the amount of binder needed is an effective amount to maintain the shape of the sleeve and allow for effective curing, i.e. which will produce a sleeve which can be handled or self-supported after curing.
  • An effective amount of binder is greater than about 4 weight percent, based upon the weight of the sleeve composition.
  • the amount of binder ranges from about 5 weight percent to about 15 weight percent, more preferably from about 6 weight percent to about 12 weight percent.
  • Curing the sleeve by the cold-box process takes place by blowing or ramming the sleeve mix into a pattern and contacting the sleeve with a vaporous or gaseous catalyst.
  • Various vapor or vapor/gas mixtures or gases such as tertiary amines, carbon dioxide, methyl formate, and sulfur dioxide can be used depending on the chemical binder chosen.
  • gaseous curing agent is appropriate for the binder used.
  • an amine vapor/gas mixture is used with phenolic-urethane resins.
  • Sulfur dioxide (in conjunction with an oxidizing agent) is used with an epoxy-acrylic resins. See U.S.
  • Patent 4,526,219 which is hereby incorporated into this disclosure by reference.
  • Carbon dioxide see U.S. Patent 4,985,489 which is hereby incorporated into this disclosure by reference
  • methyl esters see U.S. Patent 4,750,716 which is hereby incorporated into this disclosure by reference
  • Carbon dioxide is also used with binders based on silicates. See U.S. Patent 4,391,642 which is hereby incorporated into this disclosure by reference.
  • the binder is an EXACTCASTTM cold-box phenolic urethane binder cured by passing a tertiary amine gas, such a triethylamine, through the molded sleeve mix in the manner as described in U.S. Patent 3,409,579, or the epoxy-acrylic binder cured with sulfur dioxide in the presence of an oxidizing agent as described in U.S. Patent 4,526,219.
  • Typical gassing times are from 0.5 to 3.0 seconds, preferably from 0.5 to 2.0 seconds.
  • Purge times are from 1.0 to 60 seconds, preferably from 1,0 to 10 seconds.
  • the binder used was a cold-box phenolic-urethane binder as specified where the ratio of Part I to Part II was 55/45.
  • the sleeve mixes were prepared by mixing the sleeve composition and the binder in a Hobart N-50 mixer for about 2-4 minutes.
  • the sleeves prepared were cylindrical sleeves 90 mm in internal diameter, 130 mm in external diameter, and 200 mm in height.
  • the amount of binder used in all cases, except in Comparison Example A, was 8.8 weight percent based upon the weight of the sleeve composition.
  • All lettered Examples are controls where silica sand was used as the sleeve composition. All parts are by weight and all percentages are weight percentages based upon the weight of the sleeve composition unless otherwise specified.
  • silica sand One hundred parts of silica sand were used as the sleeve composition which was mixed with about 1.3 weight percent of EXACTCASTTM no-bake binder to form a sleeve mix. Then about 1 weight percent of a liquid tertiary amine, POLYCAT 41 catalyst 1 , sold by Air Products, is added to the sleeve mix. The resulting mix is shaped into cylindrical sleeves.
  • the tensile properties of the sleeves which indicates the strength of the sleeves for handling, are measured and set forth in Table I which follows.
  • the tensile strengths of the sleeves are measured immediately (30 minutes), 1 hour, 4 hours, 24 hours, and 24 hours at 100% relative humidity (RH) after removing from the corebox.
  • Example 1 One hundred parts of SG EXTENDOSPHERES were used as the sleeve composition and mixed with 8.8% of EXACTCASTTM cold-box binder to form a sleeve mix.
  • the sleeve mix of Example 1 is blown into a pattern having the shape of a sleeve and gassed with triethylamine in nitrogen at 20 psi according to known methods described in U.S. Patent 3,409,579. Gas time is 2.5 second, followed by purging with air at 60 psi for about 60.0 seconds.
  • the tensile strengths of the cured sleeves are measured as in Example 1 except the immediate tensile strength was measured 30 seconds after removing from the corebox.
  • the tensile strengths of the sleeves are set forth in Table I.
  • the sleeves are dimensionally accurate, both externally and internally.
  • Example 1 was followed except 1.2 weight percent of silicone resin was added to the sleeve mix.
  • the tensile strength of the cured sleeves are measured as in Example 1.
  • the tensile strengths of the sleeves are set forth in Table I.
  • the sleeves are dimensionally accurate, both externally and internally.
  • Example 1 The procedure of Example 1 was followed except the sleeve composition used consisted of 55% SLG EXTENDOSHPERES, 16.5% atomized aluminum, 16.5% aluminum powder, 7% magnetite, and 5% cryolite.
  • the tensile strengths of the cured sleeves are measured as in Example 1.
  • the tensile strengths of the sleeves are set forth in Table I.
  • the sleeves are dimensionally accurate, both externally and internally.
  • Example 1 The procedure of Example 1 was followed except the sleeve composition used consisted of 50% Wedron 540 silica sand, 10% alumina, and 40% of the sleeve mix of Example 3.
  • the tensile strengths of the cured sleeves are measured as in Example 1.
  • the tensile strengths of the sleeves are set forth in Table I.
  • the sleeves are dimensionally accurate, both externally and internally.
  • a sleeve composition is prepared by mixing the following components in a Hobart N-50 mixer for about 4 minutes:
  • Comparison Example B the sleeves of Comparison Example A and Examples 1-4 are tested in a casting assembly by using them to surround the top riser of the casing assembly,
  • the metal poured into the casting assembly is steel (carbon content of 0.13%) and is poured at a temperature of 1650 °C.
  • the casting of Comparison Example B made using the sleeve from Comparison Example A, experienced shrinkage and resulted in a defective casting which was scrapped as waste.
  • the castings of Examples 5-8, made with sleeves 1-4 did not shrink as Figure 4 illustrates. Figure 4 shows some shrinkage of the riser above the casting, but there was no shrinkage of the casting. In all cases, where the sleeves were made by the cold-box process, there was no shrinkage of the caseins.

Claims (21)

  1. Manchon ayant des propriétés exothermiques, des propriétés isolantes ou les deux, qui peuvent être obtenues par un procédé en boíte froide, comprenant :
    (A) l'introduction d'un mélange pour manchon dans un modèle de manchon pour la préparation d'un manchon non durci, le mélange pour manchon comprenant :
    (1) une composition pour manchon capable de former un manchon et telle que la composition pour manchon comprend :
    (a) un métal oxydable et un agent oxydant capables de créer une réaction exothermique, ou
    (b) un matériau réfractaire isolant, ou
    (c) des mélanges de (a) et (b),
    (2) une quantité efficace pour la liaison d'un liant chimiquement réactif pour boíte froide sélectionné parmi les résines phénoliques, les résines phénoliques et d'uréthanne, les liants de furanne, les liants alcalins de résols phénoliques et les liants acryliques et époxydes,
    (B) la mise en contact du manchon non durci préparé en (A) avec un catalyseur de durcissement en phase vapeur,
    (C) le durcissement naturel du manchon résultant de (B) jusqu'à ce que le manchon puisse être manié, et
    (D) l'extraction du manchon du modèle.
  2. Manchon selon la revendication 1, dans lequel le métal oxydable et le réfractaire isolant sont des matériaux contenant de l'aluminium.
  3. Manchon selon la revendication 2, dans lequel le métal oxydable contenant de l'aluminium est de l'aluminium métallique et le réfractaire isolant contenant de l'aluminium est sélectionné parmi l'alumine et un aluminosilicate.
  4. Manchon selon la revendication 3, dans lequel l'aluminium métallique est sous forme de poudre d'aluminium, de granulés d'aluminium ou des deux.
  5. Manchon selon la revendication 3, dans lequel le réfractaire isolant contenant de l'aluminium est un aluminosilicate qui est sous forme de microsphères creuses d'aluminosilicate.
  6. Manchon selon l'une quelconque des revendications 1 à 5, dans lequel la concentration de liant est comprise entre environ 4 et environ 12 % en poids par rapport au poids de la composition du manchon.
  7. Manchon selon l'une quelconque des revendications 2 à 6, dans lequel la quantité d'aluminium de la composition du manchon est comprise entre 0 et 40% en poids par rapport au poids de la composition du manchon.
  8. Manchon selon l'une quelconque des revendications 2 à 7, dans lequel un agent oxydant est présent en quantité efficace pour l'oxydation de l'aluminium métallique.
  9. Manchon selon la revendication 5, dans lequel la quantité de microsphères creuses d'aluminosilicate dans la composition du manchon est comprise entre 30 et 100 % en poids et de préférence entre 40 et 80 % en poids par rapport au poids de la composition du manchon.
  10. Manchon selon l'une quelconque des revendications 2 à 9, dans lequel la quantité d'aluminium contenue dans la composition du manchon est comprise entre 5 et 30 % en poids par rapport au poids de la composition du manchon.
  11. Manchon selon la revendication 1, dans lequel le liant chimique est un liant phénolique et d'uréthanne et le catalyseur de durcissement est une amine tertiaire en phase vapeur.
  12. Manchon selon la revendication 1, dans lequel le liant chimique est un liant acrylique et époxyde, et le catalyseur de durcissement est l'anhydride sulfureux.
  13. Manchon selon la revendication 1, dans lequel le liant chimique est une résine résol phénolique alcaline et le catalyseur de durcissement est l'anhydride carbonique.
  14. Manchon selon la revendication 1, dans lequel le liant chimique est une résine phénolique alcaline et le catalyseur de durcissement est un ester de méthyle.
  15. Manchon selon l'une quelconque des revendications 5 à 14, dont le rapport pondéral de l'aluminium métallique à l'aluminosilicate sous forme de microsphères creuses d'aluminosilicate dans la composition du manchon est compris entre 1/5 et 1/1 environ.
  16. Manchon selon l'une quelconque des revendications 1 à 15, dans lequel la composition du manchon contient un réfractaire.
  17. Manchon selon la revendication 16, dans lequel la quantité de réfractaire de la composition du manchon est comprise entre 10 et 50 % en poids par rapport au poids de la composition du manchon.
  18. Manchon selon l'une quelconque des revendications 15 à 17, dans lequel le réfractaire est la silice.
  19. Procédé en boíte froide pour la préparation de manchons qui possèdent des propriétés exothermiques, des propriétés isolantes ou les deux, comprenant :
    (A) l'introduction d'un mélange pour manchon tel que défini dans l'une quelconque des revendications 1 à 18 dans un modèle de manchon pour la préparation d'un manchon non durci,
    (B) la mise en contact du manchon non durci préparé en (A) avec un catalyseur de durcissement en phase vapeur,
    (C) le durcissement naturel du manchon résultant de (B) jusqu'à ce que le manchon puisse être manié, et
    (D) l'extraction du manchon du modèle.
  20. Application d'un manchon selon l'une quelconque des revendications 1 à 18 à un procédé de coulée d'une pièce métallique, qui comprend :
    (1) l'insertion du manchon dans un ensemble de coulée ayant un ensemble de moule
    (2) la coulée du métal, lorsqu'il est à l'état liquide, dans l'ensemble de coulée,
    (3) le refroidissement et la solidification naturelle du métal, et
    (4) la séparation ultérieure de la pièce métallique coulée de l'ensemble de coulée.
  21. Mélange pour manchon, comprenant :
    (1) une composition pour manchon capable de former un manchon, la composition pour manchon comprenant :
    (a) un métal oxydable et un agent oxydant capable de provoquer une réaction exothermique, ou
    (b) un matériau réfractaire isolant, ou
    (c) des mélanges de (a) et (b), et
    (2) une quantité efficace pour la liaison d'un liant chimiquement réactif pour boíte froide sélectionné parmi une résine phénolique, un liant phénolique et d'uréthanne, un liant de furanne, un liant de résine résol phénolique alcaline et un liant acrylique et époxyde, qui durcit en présence d'un catalyseur de durcissement en boíte froide.
EP97916916A 1996-03-25 1997-03-21 Manchons, leur preparation et utilisation Expired - Lifetime EP0888199B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BR9601454 1996-03-25
BR9601454-7A BR9601454C1 (pt) 1996-03-25 1996-03-25 Processo para produção de luvas exotérmicas e isolantes.
PCT/US1997/004628 WO1997035677A1 (fr) 1996-03-25 1997-03-21 Manchons, leur preparation et utilisation

Publications (3)

Publication Number Publication Date
EP0888199A4 EP0888199A4 (fr) 1999-01-07
EP0888199A1 EP0888199A1 (fr) 1999-01-07
EP0888199B1 true EP0888199B1 (fr) 2002-10-09

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EP97916916A Expired - Lifetime EP0888199B1 (fr) 1996-03-25 1997-03-21 Manchons, leur preparation et utilisation

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EP (1) EP0888199B1 (fr)
JP (1) JP3278168B2 (fr)
AT (1) ATE225687T1 (fr)
AU (1) AU729980B2 (fr)
BE (1) BE1010959A3 (fr)
BR (1) BR9601454C1 (fr)
CA (1) CA2221778C (fr)
DE (2) DE888199T1 (fr)
ES (1) ES2134750T3 (fr)
FR (1) FR2746332B1 (fr)
GR (1) GR1003017B (fr)
IE (1) IE970227A1 (fr)
IT (1) IT1290822B1 (fr)
NL (1) NL1005627C2 (fr)
PL (1) PL183084B1 (fr)
WO (1) WO1997035677A1 (fr)
ZA (1) ZA972479B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007012660A1 (de) 2007-03-16 2008-09-18 Chemex Gmbh Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen
DE102007031376A1 (de) 2007-07-05 2009-01-08 GTP Schäfer Gießtechnische Produkte GmbH Alternatives Cold-Box-Verfahren mit Rohölen
WO2010057464A2 (fr) 2008-11-20 2010-05-27 AS Lüngen GmbH Mélange de matière de moulage et masselotte pour coulage d'aluminium
DE202010007015U1 (de) 2010-05-20 2010-08-26 AS Lüngen GmbH Magnetischer Speiser
EP2489449A1 (fr) 2011-02-18 2012-08-22 GTP-Schäfer Giesstechnische Produkte GmbH Masselotte dotée d'un corps d'alimentation exothermique et d'une enveloppe d'isolation extérieure
DE102011079692A1 (de) 2011-07-22 2013-01-24 Chemex Gmbh Speiser und formbare Zusammensetzungen zu deren Herstellung
DE102012200967A1 (de) 2012-01-24 2013-07-25 Chemex Gmbh Speiser und formbare Zusammensetzung zu deren Herstellung enthaltend kalzinierte Kieselgur
EP2823916A1 (fr) 2013-07-10 2015-01-14 Georg Fischer GmbH Pièce moulée composite
DE102016211948A1 (de) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2134729B1 (es) * 1996-07-18 2000-05-16 Kemen Recupac Sa Mejoras introducidas en objeto solicitud patente invencion española n. 9601607 por "procedimiento para fabricacion manguitos exactos y otros elementos de mazarotaje y alimentacion para moldes de fundicion, incluyendo la formulacion para obtencion de dichos manguitos y elementos".
US6286585B1 (en) 2000-03-21 2001-09-11 Ashland Inc. Sleeve mixes containing stabilized microspheres and their use in making riser sleeves
US6335387B1 (en) 2000-03-21 2002-01-01 Ashland Inc. Insulating sleeve compositions containing fine silica and their use
NO20065286L (no) * 2006-11-17 2008-05-19 Elkem As Refractory dry powder for ladle and furnace linings for metallurgical vessels
RU2512517C2 (ru) * 2008-01-31 2014-04-10 ЭШЛЭНД ЛАЙСЕНСИНГ ЭНД ИНТЕЛЛЕКТЧУАЛ ПРОПЕРТИ ЭлЭлСи Композиции, содержащие определенные металлоцены, и их применение
DE102012019802B4 (de) 2012-10-10 2023-07-27 Mercedes-Benz Group AG Verfahren zur Herstellung eines Gusskörpers
CN103878307A (zh) * 2012-12-21 2014-06-25 南通太和机械集团有限公司 一种p形铸造模具
US10105755B2 (en) 2014-07-14 2018-10-23 Gf Casting Solutions Mettmann Gmbh Composite casting part
EP3756787B1 (fr) 2019-06-24 2022-05-04 GTP Schäfer Gießtechnische Produkte GmbH Insert d'alimentation à gaine
EP3756788A1 (fr) 2019-06-24 2020-12-30 GTP Schäfer Gießtechnische Produkte GmbH Insert d'alimentation doté d'un contour extérieur avant et arrière
DE102020131492A1 (de) 2020-11-27 2022-06-02 Chemex Foundry Solutions Gmbh Herstellverfahren, Gießformen, Kerne oder Speiser sowie Kit und Verfahren zur Herstellung eines metallischen Gussteils.
TR2022014215A2 (tr) * 2022-09-14 2022-10-21 Erkunt Sanayi Anonim Sirketi Ekzotermi̇k besleyi̇ci̇ üreti̇m yöntemi̇

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB922505A (en) * 1961-02-16 1963-04-03 Distillers Co Yeast Ltd Production of foundry moulding shapes
US3485797A (en) * 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3429848A (en) * 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
DE2121353A1 (en) * 1971-04-30 1972-11-09 Baur, Eduard, Dipl.-Ing., 5256 Waldbruch Casting mould riser insert - made from globular insulating material giving improved casting
SU865119A3 (ru) * 1977-07-28 1981-09-15 Хута Косьцюшко Пшедсембиоратво Паньствове (Инопредприятие) Теплоизол ционна смесь дл изготовлени плит в прибыльных надставках сталеразливочных изложниц
ZA792535B (en) 1978-05-30 1980-06-25 Foseco Trading Ag Heat-insulating articles
US4268425A (en) * 1979-05-14 1981-05-19 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a drying oil and use thereof
US4526219A (en) * 1980-01-07 1985-07-02 Ashland Oil, Inc. Process of forming foundry cores and molds utilizing binder curable by free radical polymerization
GB8610739D0 (en) * 1986-05-01 1986-06-04 Foseco Int Exothermic compositions
GB9308363D0 (en) * 1993-04-22 1993-06-09 Foseco Int Refractory compositions for use in the casting of metals

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007012660A1 (de) 2007-03-16 2008-09-18 Chemex Gmbh Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen
DE102007012660B4 (de) * 2007-03-16 2009-09-24 Chemex Gmbh Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen
DE102007031376A1 (de) 2007-07-05 2009-01-08 GTP Schäfer Gießtechnische Produkte GmbH Alternatives Cold-Box-Verfahren mit Rohölen
WO2010057464A2 (fr) 2008-11-20 2010-05-27 AS Lüngen GmbH Mélange de matière de moulage et masselotte pour coulage d'aluminium
DE102008058205A1 (de) 2008-11-20 2010-07-22 AS Lüngen GmbH Formstoffmischung und Speiser für den Aluminiumguss
DE202010007015U1 (de) 2010-05-20 2010-08-26 AS Lüngen GmbH Magnetischer Speiser
EP2489449A1 (fr) 2011-02-18 2012-08-22 GTP-Schäfer Giesstechnische Produkte GmbH Masselotte dotée d'un corps d'alimentation exothermique et d'une enveloppe d'isolation extérieure
DE102011079692A1 (de) 2011-07-22 2013-01-24 Chemex Gmbh Speiser und formbare Zusammensetzungen zu deren Herstellung
WO2013014118A2 (fr) 2011-07-22 2013-01-31 Chemex Gmbh Masselottes et compositions façonnables pour la fabrication desdites masselottes
DE102012200967A1 (de) 2012-01-24 2013-07-25 Chemex Gmbh Speiser und formbare Zusammensetzung zu deren Herstellung enthaltend kalzinierte Kieselgur
EP2823916A1 (fr) 2013-07-10 2015-01-14 Georg Fischer GmbH Pièce moulée composite
DE102016211948A1 (de) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen
WO2018002027A1 (fr) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Particules cœur-écorce destinées à être utilisées comme charge dans des matières pour masselottes

Also Published As

Publication number Publication date
AU729980B2 (en) 2001-02-22
NL1005627C2 (nl) 1998-07-27
EP0888199A4 (fr) 1999-01-07
IT1290822B1 (it) 1998-12-11
EP0888199A1 (fr) 1999-01-07
ZA972479B (en) 1998-09-25
FR2746332B1 (fr) 1999-05-28
BR9601454A (pt) 1999-07-27
JP3278168B2 (ja) 2002-04-30
ES2134750T1 (es) 1999-10-16
CA2221778C (fr) 2004-06-01
NL1005627A1 (nl) 1997-10-03
DE69716248T2 (de) 2003-08-07
PL183084B1 (pl) 2002-05-31
AU2540697A (en) 1997-10-17
ITMI970688A1 (it) 1998-09-25
CA2221778A1 (fr) 1997-10-02
BE1010959A3 (fr) 1999-03-02
BR9601454C1 (pt) 2000-01-18
JP2000501028A (ja) 2000-02-02
WO1997035677A1 (fr) 1997-10-02
PL328966A1 (en) 1999-03-01
ATE225687T1 (de) 2002-10-15
ES2134750T3 (es) 2003-03-01
GR970100095A (el) 1997-11-28
DE888199T1 (de) 2000-02-17
GR1003017B (el) 1998-11-26
DE69716248D1 (de) 2002-11-14
FR2746332A1 (fr) 1997-09-26
IE970227A1 (en) 2000-10-04

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