IE970227A1

IE970227A1 - Sleeves, their preparation and use

Info

Publication number: IE970227A1
Application number: IE19970227A
Authority: IE
Inventors: Paulo Roberto Menon
Original assignee: Ashland Inc
Priority date: 1996-03-25
Filing date: 1997-03-24
Publication date: 2000-10-04
Also published as: AU729980B2; NL1005627C2; EP0888199A4; IT1290822B1; EP0888199A1; ZA972479B; FR2746332B1; BR9601454A; JP3278168B2; ES2134750T1; CA2221778C; NL1005627A1; DE69716248T2; PL183084B1; AU2540697A; ITMI970688A1; CA2221778A1; BE1010959A3; BR9601454C1; JP2000501028A

Abstract

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 chemical binder into a sleeve. The sleeves are cured in the presence of a catalyst by the cold-box or no-bake 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. Additionally, the invention relates to the metal parts produced by the casting process.

Description

SLEEVES, THEIR PREPARATION, AND USE FIELD OF THE INVENTION 1 This invention relates to exothermic and/or insulating sleeves, their method of s preparation, and their use. The sleeves are prepared by shaping a sleeve mix comprising (I) 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 or no-bake 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. Additionally, the io invention relates to the metal parts produced by the casting process.

BACKGROUND OF THE INVENTION A casting assembly consists of a pouring cup, a gating system (including downsprues, choke, and runner), risers, sleeves, molds, cores, and other components. To is produce a metal casting, metal is poured into the pouring cup of the casting assembly and passes through the gating system to the mold and/or core assembly where it cools and solidifies The metal part is then removed by separating it from the core and/or mold assembly.

The molds and/or cores used in the casting assembly are made of sand or other 20 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/nxK. 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.

OPEN TO PUBLIC INSPECTION UNDER SECTION 28 AND RULE 23 JNL MOL, .OF X Cfri *»·< I Risen or feeders are reservoirs which contain excess mohen 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. Thus the metal from the riser is allowed to remain in a liquid state for a longer period of s time, thereby providing metal to the casting as it cools and solidifies. 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 are used to surround or encapsulate the riser and other parts of the casting io assembly in order to keep the molten metal in the riser hot and maintain it in the liquid state In order to accomplish this, the sleeves must have exothermic and/or insulating properties. The exothermic and insulating thermal properties of the sleeve are different in kind anchor degree than the thermal properties of the mold assembly into which they are inserted. Predominately exothermic sleeves operate by liberating heat which increases the temperature of the molten metal in the riser, thereby keeping the metal hot and liquid longer. Insulating sleeves, on the other hand, 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 mohen metal hot and liquid. Compositions used in foundry molds and cores are not useful for making sleeves because they are denser and their thermal properties are not appropriate.

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 to 0.8 g/ml while the thermal conductivity depends upon whether exothermic or insulating properties are wanted in the sleeve. Thermal conductivity for aluminum is typically greater than 200 while the thermal conductivity for hollow aluminosilicate microspheres at room temperature ranges from 0.05 to 0.5 W/tn.K. To some extent, all sleeves are required to have insulating properties, or combined insulating and exothermic properties in order co minimize heat loss aod co maintain the metal in a liquid state for as long a time as possible.

Three basic processes are used for the production of sleeves, ramming, vacuuming, and blowing or shooting. 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 and form a sleeve. Typically, whether ramming, blowing, or vacuuming is used to form the sleeve shape, the sleeves formed are oven-dried to remove contained water and cure the shaped binder/sleeve composition. 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.

These 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 Q>ers 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 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.

Another problem with sleeves is that they 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 castings experience shrinkage which results in casting defects and waste. When these casting defects occur, they must be eliminated by machining 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.

SUMMARY OF THE INVENTION This invention relates to a no-bake and cold-box process for making exothermic and/or insulating sleeves, the sleeves made by this method, and the use of the sleeves in making metal castings. Typically, the steps involved in preparing a sleeve are: (A) introducing a sleeve mix into a sleeve pattern to form an uncured sleeve wherein said sleeve mix comprises: (1) a sleeve composition capable of making a sleeve wherein the sleeve composition comprises: (a) an oxidizable metal and an oxidisinq agent capable of generating an exothermic reaction; (b) an insulating refractory material; and (c) mixtures of (a) and (b); (2) an effective binding amount of a chemically reactive cold-box binder, (B) contacting the uncured sleeve with a no-bake or cold-box catalyst to allow the sleeves to become self-supporting; and (C) removing said sleeve from the pattern and allowing rt to further cure and become a hard, solid, cured sleeve.

In the no-bake process, the curing catalyst is a liquid and is mixed with the sleeve mix, binder, and other components prior to shaping. In the cold-box process, the sleeve mix is first shaped and then contacted with a vaporous curing catalyst. The components of the no-bake and cold-box sleeve mixes are uniformly mixed so that the mixture maintains io its consistency.

The no-bake and cold-box processes result in chemically cured sleeves. The processes result 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 Sbers wbicb cause breathing problems when ingested.

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 de 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 shrink. This eliminates defects which require machining of the casting and/or wasted castings. s 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 process made using these sleeves results in less waste because the sleeves enable the mohen metal in the reservoir of the sleeve riser to be reduced compared to the molten metal contained in the reservoir of a traditional 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.

BRIEF DESCRIPTION OF THE FIGURES s Figure I 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.

DEFINITIONS o The following definitions will be used for terms in the disclosure and claims: Casting assembly - assembly of casting components such as pouring cup, downsprue, gating system (downsprue, runner, choke), molds, cores, risers, sleeves, etc. which are used to make a metal casting by pouting molten metal into the casting assembly where it flows to the mold assembly and cools to form a metal part.

Chemical binding - binding created by the chemical reaction of a catalyst and a binder which is mixed with a sleeve composition.

Cold-box mold or core making process which utilizes a vaporous catalyst to cure the mold or core. s Downsprue main feed channel of the casting assembly through which the molten is poured.

EXACTCAST™ cold-box binder a two part polyurethane-forming cold-box binder where the Part I is 10 a phenolic resin similar to that described in U.S. Patent 3,485,797 is dissolved in a blend of aromatic, ester, and aliphatic solvents, a benchlife extender, and a silane. Part H is the polyisocyanate component comprising pofymethyfene polypheny! isocyanate and a solvent blend consisting primarily of aromatic solvents and a minor amount of aliphatic solvents. The weight ratio of Part I to Part II is about 55:45.

EXACTCAST™ no-bake binder a two part polyurethane-forming πο-bake binder which is similar to 20 the EXACTCAST™ cold-box binder. EXACTCAST™ no-bake binder does not contain a benchlife extender or silane. Exothermic sleeve - a sleeve which has exothermic properties compared to the mdd/core assembly into which it is inserted. The exothermic properties of the 25 sleeve are generated by an oxidizable metal (typically aluminum metal) and a reducible metal oxide which can react to generate heat. EXTENDOSFHERES SG -hollow aluminosilicate microspheres sold by PQ Corporation having a particle size of 10-350 microns and an alumina content between 30 28% to 33% by weight based upon the weight of the microspheres. 7 I extendosfheres slg -hollow aluminosilicate microspheres sold by PQ Corporation having a particle size of 10-300 microns and an alumina content of at least 40% by weight based upon the weight of the microspheres. Gating system system through which metal is transported from the pouring cup to the mold and/or cote assembly. Components of the gating system include the downsprue, runners, choke, etc. Handleable - sleeve which can be transported from one place to another without sagging or breaking.

Insulating refractory material - a refractory material with a thermal conductivity typically less than about 0.7 W/m.K at room temperature, preferably less than about 0.5 W/m.K. Insulating sleeve - a sleeve having greater insulating properties than the mokVcore assembly into which it is inserted. An insulating sleeve typically contains low density materials such as fibers and/or hollow microspheres. Mold assembly an assembly of molds and/or cores made from a foundry aggregate (typically sand) and a foundry binder, winch is placed in a casting assembly to provide a shape for the casting. No-bake - mold or core making process which utilizes a liquid catalyst to cure the mold or core. Pouring cup - cavity through which molten metal is poured into the casting assembly.

Refractory - a ceramic type material having a thermal conductivity greater than about 0.8 W/m_K at room temperature which is capable of withstanding extremely high temperatures without essential change when it comes into contact with molten metal which may have a s temperature as high as, for instance, ί 70Q°C.

Riser - cavity connected to a mold or casting cavity of the casting assembly which acts as a reservoir for excess molten metal to prevent cavities in the casting as it contracts on solidification. Risers may be open or io blind. Risers are also known as feeders or heads.

Sleeve - any moldable shape having exothermic and/or insulating properties made from a sleeve composition which covers, in whole or part, any component of the casting assembly such as the riser, runners, pouring is cup, sprue, etc. or is used as part of the casting assembly. Sleeves can have a variety of shapes, e.g. cylinders, domes, cups, boards, cores.

Sleeve composition - any composition which is capable of providing a sleeve with exothermic and/or insulating properties. The sleeve composition will usually contain aluminum metal and/or aluniunosilicate, particularly in the form of hollow aluminosilicate microspheres, or mixtures thereof Depending upon the properties wanted, the sleeve composition may also contain alumina, other refractory material, an oxidizing agent, fluorides, fibers, and fillers.

Sleeve mix - a mixture comprising a sleeve composition and a chemical binder capable of forming a sleeve by the no-bake or cold-box process.

I DETAILED DESCRIPTION OF FIGURES Figure I shows a simple casting assembly comprising pouring cup 1, sprue 2, runner 3, sleeve for ride riser 4, ride riser 5, sleeve for top riser 6, top riser 7, and β 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 mold and core assembly 3. 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.

I 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 is and the metal of the casting 3. This casting is defective and will be scrapped as waste Figure 4 illustrates a 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, DESCRIPTION OF BEST MODE AND OTHER MODES FOR PRACTICING THE INVENTION The sleeve mixes used in the subject process contain (1) a sleeve composition, and 25 (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.

There is nothing novel about the sleeve composition used for making the exothermic and/or insulating sleeves. Any sleeve composition known in the art for making sleeves can be used to make the sleeves. The sleeve composition contains exothermic and/or insulating materials, typically inorganic. The exothermic and/or insulating materials typically are I aiuminum-containing materials, preferably selected from the group consisting of aluminum metal, aluminosilicate, alumina, and mixtures thereof most preferably where the ahuranosiheate is in the form of hollow microspheres.

The exothermic material is an oxidizable metal and an oxidising agent capable 5 of generating an exothermic reaction at the temperature where the metal can be poured.

The oxidizable metal typically is aluminum in either powder or granule form, but magnesium and similar metals can also be used. The insulating material is. typically aluminosilicate, preferably aluminosilicate in the form of hollow microspheres, and possibly alumina.

When aluminum metal is used as the oxidizable metal for the exothermic sleeve, it is io typically used in the form of aluminum powder or aluminum granules. The oxidising agentused for the exothermic sleeve includes, iron oxide, permanganate, etc. Oxides do not need to be present at stoichiometric levels to satisfy the metal aluminum fuel component. This is because the riser sleeves and molds in which they are contained are permeable. Thus oxygen from the oxides is supplemented by atmospheric oxygen winch results when the is aluminum fuel is burned. Typically 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 conductivity of the exothermic sleeve is such that heat will be generated to raise the temperature of the molten metal in the riser, thereby’ keeping it hot and liquid. The exotherm results from the reaction of aluminum and the oxidizing agent in the exothermic sleeve mix when it comes into contact with the molten metal. A mold and/or core does not exhibit exothermic properties.

As was mentioned before, the insulating properties of the sleeve are preferably . provided by hollow aluminosilicate microspheres, including aluminosilicate zeeospheres.

The sleeves made with aluminosilicate hollow microspheres have a lower density, lower 25 thermal conductivities, and better insulating properties. The exothermic sleeves have higher thermal conductivity than the insulating sleeves. 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.

Depending upon the degree of exothermic properties wanted in the sleeve, 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.

Depending upon the degree of insulating properties wanted in the sleeve, the amount of aluminosilicate, particularly in the form 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 w eight of the sleeve composition. Since in most cases, both insulating and exothermic properties are needed in the sleeves, both io 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 111 to about 1:2, preferably from about 1:1 to about 1:1.5.

The hollow aluminosilicate microspheres typically have a particle size of about 3 is 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 other material having insulating properties can also be used to replace or in combination with the hollow aluminosilicate microspheres. o The weight percent of alumina to silica (as SiO;) in the hollow aluminosilicaie 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 in the melting of 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 them 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 skxve mixture so the sleeve will not degrade when it comes into contact with the molten metal during the casting process. Examples of such 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 When 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.

In addition, the sleeve composition may contain different fillers and additives, such as cryolite (NajAJFi), potassium aluminum tefrafluoride, potassium aluminum hexafluoride.

The density of the sleeve composition typically ranges from about 0,1 to about 0.9 is g/cc, more typically from about 0.2 to about Q.& g/cc . For exothermic sleeves, the density of the sleeve composition typically ranges from about 0.3 to about 0.9 g/cc, more typically from about 0.5 to about 0.8 g/cc. For insulating sleeves, the density of the sleeve composition typically ranges from about 0.1 to about 0.7 g/cc, more typically from about 0.3 to about 0.6 g/cc. For exothermic sleeves, the thermal conductivity of the sleeve composition typically is greater than 150 W/m.K at room temperature, more typically greater than 200 W/m.K. For insulating sleeves, the thermal· conductivity of the sleeve composition typically ranges from about 0.05 to about 0.6 W/m.K at room temperature, more typically from about 0.1 to about 0.5 W/m_K.

The binders that are mixed with the sleeve composition to form the sleeve mix are well know in the art. Any no-bake or 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 wort. Examples of such binders are phenolic resins, phenolic urethane binders, furan binders, alkaline phenolic resole binders, and epoxy-acrylic binders among others. Particulariy preferred are phenolic urethane binders known as EXACTCAST™ cold-box binder sold by Ashland Chemical Company Binders like these 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 amount of binder needed is an effective amount to maintain the shape of the sleeve and allow for effective curing. Le. which will produce a sleeve which can be handled or seif-supported after curing. An effective amount of binder is greater than about 2 weight percent, more likely greater than about 3 weight percent, based upon the weight of the sleeve composition. Preferably the amount of binder ranges from about 4 weight io percent to about 12 weight percent, more preferably from about 5 weight percent to about 10 weight percent.

Curing the sleeve by the no-bake process takes place by mixing a liquid curing catalyst with the sleeve mix (alternatively by mixing the liquid curing catalyst with the sleeve composition first), shaping the sleeve mix containing the catalyst, and allowing the sleeve is shape to cure, typically at ambient temperature without the addition of heat. The preferred liquid curing catalyst is a tertiary amine, and the preferred no-bake curing process are described in U.S. Patent 3,485,797 which is hereby incorporated by reference into this disclosure. Specific examples of such liquid curing catalysts indude 4-alkyl pyridines wherein the alkyl group has fioru one to four carbon atoms, isoqtnnoSne, arylpyritfctes sach as phenyl pyridine, pyridine, acridine, 2-mefooxypyridine, pyridazine, 3-chloro pyridine, quinoline, Nmethyl imidazole, N-ethyl imidazole, 4,4’-drpyridme, 4-phenyfpropyipyridine, Imethylbenziinidazole, and 1,4-thiazine.

Curing the sleeve by the cold-box process takes place by blowing or ramming the sleeve mix into a pattern box and contacting the sleeve shape with a vaporous or gaseous catalyst. Various gases such as tertiary amines, carbon dioxide, methyl formate, and sulfur dioxide can. be used depending on the chemical hinder chosen. Those skilled in the art will • know which gaseous curing agent is appropriate for the binder used. For example, an amine gas 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) or methyl esters (see U. S. Patent 4,750,716) which is hereby incorporated into this disclosure by reference) are used with alkaline phenolic resole resins. Carbon dioxide is also used with binders based on S silicates. See U.S. Patent 4,391,642 which is hereby incorporated into this disclosure by reference.

Preferably the binder is an EXACTCAST™ cold-box binder, as mentioned before, ' and curing is affected by passing a tertiary amine gas, such a triethyiamine, through the molded sleeve mix in the manner as described in U.S. Patent 3,409,579, which is hereby incorporated io into this disclosure by reference. 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 30 seconds, preferably from 1.0 to 10 seconds.

EXAMPLES j 5 In all of the examples which fellow the sleeve compositions as specified were prepared by mixing the components in a Hobart N-50 mixer for about 2-4 muxites. The binder used was either & no-bake or cold-box phenolic-urethane binder as specified where the ratio of Part I to Part Π was 55/45. The sleeve mixes were prepared by mixing the sleeve composition and the binder a Hobart N-50 mixer for about 2-4 minutes. In the no-bake sleeve compositions, the liquid curing catalyst is added to the sleeve mix before shaping. The sleeves prepared were Cylindrical sleeves 90 nun in internal diameter, 130 nun 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. AH 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.

COMPARISON EXAMPLE A (Sleeve formed from silica sand.) is One hundred parts of silica sand were used as the sleeve composition which was mixed with about 1.3 weight percent of EXACTCAST™ no-bake binder to form a sleeve mix. Then about I weight percent of a liquid tertiary amine, POLYCAT 41 catalyst1 (2..6¾ active based upon the Part I), 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 30 minutes, 1 hour, 4 hours, 24 hours, and 24 hours at 100% relative humidity (KH) after miring with POLYCAT 41 catalyst.

Although the tensile strengths were good, steel castings made with the sleeves experienced shrinkage which is represented by Figure 3. The shrinkage occurred because the thermal properties were not adequate for sleeve applications. These castings were defective and were scrapped.

EXAMPLE 1 (Preparation of insulating sleeve by no-bake method) The no-bake process of Comparison Example A was followed except 100 parts of SG EXTENDOSPHERES were used as the sleeve composition and mixed with 8.8% of EXACTCAST™ no-bake binder to form a sleeve mix. Then about 1 weight percent of a liquid tertiary amine, POLYCAT 41 catalyst is added to the sleeve mix. The resulting nrix is shaped into a sleeve.

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, 1 hour, and 24 hours after mixing with EXACTCAST™ no-bake binder.

The sleeves are dimenscnaiiy accurate, both externally and internally.

EXAMPLE 2 :Less than 5.% active based upon the Part L I (Preparation of insulating sleeve containing hollow aluminosilicate mjerospheres by cold-box method) One hundred parts of SG EXTENDOSPHERES were used as the sleeve composition 5 and mixed with 8.8% of EXACTCAST™ cold-box binder to form a sleeve mix. The sleeve mix of Example 2 is blown into a chamber 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 al 60 psi for about 60.0 seconds.

The tensile strength of the cured sleeves are measured as in Example 1. The tensile strengths of the sleeves are set fort in Table I. The sleeves are dimensionally accurate, both externally and internally.

EXAMPLE 3 (Example 2 with silicone resin.) Example 2 was followed except 1.2 weight percent of sffieone resin was added to the sleeve mix. The tensile strength of the cured sleeves are measured as in Example I. The tensile strengths of the sleeves are set fort in Table I. The sleeves are dSmensionaffy accurate, both externally and internally.

EXAMPLE 4 (Preparation of exothermic sleeve by the cold-box method.) The procedure of Example 2 was followed except the sleeve composition used consisted of 55% SLGEXTENDOSHPERES, 16.5% atomized aluminum, 16.5 aluminum powder, 7% magnetite, and 5% cryolite 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 5 (Preparation of exothermic sleeve containing silica by the no-bake method.) The procedure of Example 1 was followed except the sleeve composition used consisted of 50% W edr on 540 silica sand, 10% alumina, and 40% of the sleeve mix of Example 4. 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 6 (Preparation of exothermic sleeve containing silica by the cold-box method.) l o The procedure of Example 2 was followed except the sleeve composition used consisted of 50% Wedron 540 silica sand, 10% alumina, and 40% of the sleeve mix of Example 4. 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 7 (Sleeve composition.) A sleeve composition is prepared by mixing the following components a Hobart N50 mixer for about 4 minutes: 50% silica sand, % iron oxide, % alumina, . 3% sodium nitrate, % aluminum, powder, and 2% sawdust The sleeve composition is used to prepare cylindrical sleeves the no-bake or cold-box method. Exothermic and insulating properties of the sleeves are varied by changing the amount of aluminum metal and alumina TABLE I (Properties of Test Shapes) TENSILE STRENGTHS GF SLEEVES EXAMPLE aLEZVS. 30 min. 1 hour 4 hours 24 hours @ 100% RH DIM. ACC. Conpariscn B A 208 224 250 290 59 accurate 9 I 41 119 129 132 65 accurate 10 2 133 183 193 212 147 acenrate 11 3 140 208 220 232 230 accurate 12 5 88 69 105 96 88 accurate 13 6 41 101 99 129 70 accurate 14 7 99 140 106 144 125 accurate EXAMPLES 15-20 In Comparison Example C, and Examples 15-20, the sleeves of Comparison Example A and Examples 1-6 are tested in a casting assembly by using them to surround the top riser of the casting assembly. The metal poured into the casting assembly is steel and is poured at a temperature of 1650 °C. The casting of Comparison Example C, made using io the sleeve from Comparison Example A experienced shrinkage and resulted in a defective casting which was scrapped as waste. The castings of Examples 15-20, made with sleeves 1-7, did not shrink as Figure 4 illustrates. Figure 4 shows some shrinkage of the riser above the casting, but the castings can still be used effectively. In all cases, where the sleeves were made by the cold-box and no-bake process, there was no shrinkage of the casting. is These results are summarized in Table Π which follows.

TABLE Π CASTING RESULTS EXAMPLE SLEEVE CAJSTIISG RESULTS Comparison C A Shrinkage of casting resulting in casting defect and waste. 15 I No shrinkage of casting No waste or casting defect resulted. 16 2 No shrinkage of casting. No waste or casting defect resulted. 17 3 No shrinkage of casting. No waste or casting defect resulted. 18 4 No shrinkage of casting. No waste or casting defect resulted. 19 6 No shrinkage of casting. No waste or casting defect resulted. 20 7 No shrinkage of casting. No waste or casting defect resulted.

Claims

1.CLAIMS A cold-box process For preparing sleeves that have exothermic properties, insulating properties, or both, comprising: (A) introducing a sleeve mix into a sleeve pattern wherein said sleeve mix comprises: (1) a sleeve composition capable of making a sleeve wherein said sleeve composition comprises: (a) an oxidizable metal and an oxidising agent capable of generating an exothermic reaction; or (b) an insulating refractory material; or (c) mixtures of (a) and (b);

2. (2) an efiective landing amount of a chemically reactive cold-box binder; (B) forming a sleeve by introducing said sleeve mix into a sleeve pattern; (C) contacting said sleeve prepared by (B) with a vaporous curing catalyst; (D) allowing said sleeve resulting from (C) to cure until said shape becomes handleable; and (E) removing the shape from the pattern. 2. The process of claim I wherein the oxidizable metal and the insulating refractory are aluminum-containing materials.

3. The process of claim 2 where the oxidizable metal is aluminum metal and the 5 insulating refractory is selected from the group consisting of alumina and aluminosilicate.

4.The process of claim 3 wherein the aluminum metal is in the form of aluminum powder or aluminum granules. io

5. The process of claim 4 where the insulating refractory is aluminosilicate which is in the form of hollow aluminosilicate microspheres.

6. The process of claim 5 wherein the hinder is selected from the group consisting of is phenolic urethane binders and epoxy-acrylic binders.

7. The process of claim 6 wherein the binder level is from about 4 weight percent to about 12 weight percent based upon the weight of the sleeve composition. 20

8. The process of claim 7 wherein the amount of aluminum metal in the sleeve composition is from 0 weight percent to 40 weight percent based upon the weight of the sleeve composition.

9. The process of claim 8 wherein an oxidizing agent is present in amount effective to 2 5 oxidize any aluminum metal in the sleeve composition.

10. The process of claim 9 wherein the amount of hollow aluminosilicate microspheres in the sleeve composition, is from 30 weight percent to 100 weight percent based upon the weight of the sleeve composition.

11. The process of claim 10 wherein the amount of aluminum metal in the sleeve composition is from 5 weight percent to 30 weight percent based upon the weight of the sleeve composition. s

12. The process of claim 11 wherein the amount of alumina in the hollow aluminosilicate microspheres in the sleeve composition is from 40 weight percent to 80 weight percent based upon the weight of the sleeve composition

13. The process of claim 12 whetein the chemical binder is a phenolic· urethane binder io and the curing catalyst is a vaporous tertiary amine.

14. The process of claim 13 wherein the chemical binder is an epoxy-acrylic binder and the curing catalyst is sulfur dioxide. is

15. The process of claim 13 wherein the weight ratio of aluminum metal to aluminosilicate in the Form of hollow aluminosilicate microspheres in the sleeve composition is from is from about 1:1 to about 1:5.

16. The process of claim 15 wherein the sleeve composition contains a refractory.

17. The process of claim 16 wherein the refractoiy material is silica.

18. The process of claim 17 wherein the weight ratio of the aluminum containing material to refractory material is from 10:100 to 50:100.

19. A no-bake process for preparing sleeves having exothermic properties, insulating properties, or both which are chemically cured in the presence of a liquid catalyst comprising the steps of: (A) introducing a sleeve mix into a sleeve pattern to form a sleeve wherein said sleeve mix comprises: (1) a sleeve composition capable of making a sleeve wherein the sleeve 5 composition comprises: (a) an oxidizable metal and a n oxidising agent capable of generating an exothermic reaction; or (b) an insulating refractory material; or (c) mixtures of (a) and (b); (2) an effective binding amount of a chemically reactive no-bake binder, is and (3) a catalytically effective amount of liquid catalyst; (B) allowing the sleeve resulting from (A) to cure until said shape becomes 20 handleable; and (C) removing the shape from the pattern.

20. The process of claim 19 wherein the oxidizable metal and the insulating refractory 2 5 are aluminum-containing materials.

21. The process of claim 20 where the aluminum-containing oxidizable metal is aluminum metal and the aluminum-containing insulating refractory is selected from the group consisting of alumina and aluminosilicate.

22. The process of claim 21 wherein the aluminum metal is in the form of aluminum powder or aluminum granules.

23. The process of claim 22 where the refractory is aluminosilicate which is in the form 5 of hollow aluminosilicate microspheres.

24. The process of claim 23 wherein the binder is a phenolic urethane binder.

25. The process of claim 24 wherein the hinder level is from about 4 weight percent to 10 about 12 weight percent based upon the weight of the sleeve composition.

26. The process of claim 25 wherein the amount of aluminum in the sleeve composition is from 0 weight percent to 40 weight percent based upon the weight of the sleeve composition.

27. The process of claim 26 wherein an oxidizing agent is present in an amount effective to oxidize the aluminum metal.

28. The process of claim 27 wherein the amount of hollow aluminosilicate microspheres 20 in the sleeve composition is from 30 weight percent to 100 weight percent based upon the weight of the sleeve composition.

29. The process of claim 28 wherein the amount of aluminum in the sleeve composition is from 5 weight percent to 30 weight percent based upon the weight of the sleeve 25 composition.

30. The process of claim 29 wherein the amount of hollow aluminosilicate microspheres, in the sleeve composition is from 40 weight percent to 80 weight percent baaed upon the weight of the sleeve composition.