WO1997018913A1 - Procede en boîte froide servant a preparer des formes de fonderie - Google Patents

Procede en boîte froide servant a preparer des formes de fonderie Download PDF

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Publication number
WO1997018913A1
WO1997018913A1 PCT/US1996/018595 US9618595W WO9718913A1 WO 1997018913 A1 WO1997018913 A1 WO 1997018913A1 US 9618595 W US9618595 W US 9618595W WO 9718913 A1 WO9718913 A1 WO 9718913A1
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WO
WIPO (PCT)
Prior art keywords
foundry
shape
weight
phenol
preparing
Prior art date
Application number
PCT/US1996/018595
Other languages
English (en)
Inventor
Santiago Prat Urreiztieta
Marco Antonio Mendizabel Castellanos
Original Assignee
Ashland Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Inc. filed Critical Ashland Inc.
Priority to AU10787/97A priority Critical patent/AU1078797A/en
Publication of WO1997018913A1 publication Critical patent/WO1997018913A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening
    • B22C9/123—Gas-hardening

Definitions

  • the invention relates to a cold-box process for preparing foundry shapes.
  • the process involves curing a foundry shape by subjecting it to carbon dioxide and heat.
  • the foundry shape is made by mixing an aggregate with a foundry binder comprising: (a) an aqueous basic solution of a phenolic resole resm, and (b) preferably a compound which is a source of an oxyanion.
  • the invention also relates to a process of making metal castings with the foundry shapes.
  • foundry shapes are prepared by mixing an aggregate with the alkaline phenolic resole resin, but the foundry shape is cured by contacting the foundry shape with carbon dioxide. This results in a process which creates less stress to the environment, but which produces foundry shapes with inferior tensile strengths and scratch hardness than those produced by the process using methyl formate.
  • patent 5,162,393 also describes improved performance of these binders when a pressurized core box with carbon dioxide is used in the process.
  • improvements there still is a need to improve the physical properties of foundry shapes made with binders cured with carbon dioxide, particularly since these processes require longer gassing times, such as from 30 to 60 seconds to produce workable foundry shapes. These longer gassing time result in slower cycle times and decreased productivity result.
  • the foundry shape (b) contacting the foundry shape of (b) with carbon dioxide gas and a source of heat at a temperature of 20°C to 100°C; and (d) allowing the foundry shape to harden into a workable foundry shape.
  • the source of heat is the tooling of the corebox.
  • Foundry shapes made by this process show improved scratch hardness without sacrificing tensile strengths when compared to foundry shapes made without heating the foundry shape. Improved scratch hardness is particularly important when making bulky cores, for instance cores weighing 0.1 to 100 kilograms and having dimensions of from 5 X 5 X 5 cm 3 to 100 X 100 X 100 cm 3 . Other properties of the cores are not sacrificed even when shorter gassing times are used, for e.g. from 1 second to 30 seconds. Because gassing time can be reduced, productivity can be increased by reducing cycle times.
  • a "foundry shape” is a shape used in pouring metal castings and is made by shaping a mixture of a foundry aggregate and a binder.
  • Such shapes include cores, molds, and assemblies of cores and molds.
  • the "cold-box process” refers to a process for making foundry shapes wherein a foundry mix is formed by mixing an aggregate and a binder and cured with a gas curing agent.
  • the foundry mix is mechanically forced into a corebox where it is cured to form a foundry shape.
  • the cold-box process is particularly useful for smaller foundry shapes such as cores weighing from about 100 g to about 100 kg, typically from about 1 kg to about 50 kg.
  • aqueous basic solutions of phenolic resole resins used in the subject binder compositions are prepared by methods well known in the foundry art.
  • the specific method for preparing the aqueous solutions of phenolic resole resins is not believed to be critical to the effective practice of this invention. Those skilled in this art will know what conditions to select depending upon the specific application.
  • the general procedure involves reacting an excess of an aldehyde with a phenolic compound in the presence of a basic catalyst at temperatures of about 40 ⁇ C to about 120°C, typically from about 50 C C to about 90°C, to prepare a phenolic resole resin. Generally the reaction will also be carried out in the presence of water. Preferably, the resulting phenolic resole resin is diluted with a base and/or water so that an aqueous basic solution of the phenolic resole resin results having the following characteristics:
  • Aqueous basic solutions with a solids content below the cited range will not sufficiently coat the aggregate while those having a solids content above the cited range will not be sufficiently flowable in the molding equipment.
  • the equivalent ratio specified for the base relates co tne need tor having solutions which have adequate shelf stability.
  • the phenolic compounds used to prepare the phenolic resole resins can be represented by the following structural formula:
  • aldehyde used in preparing the phenolic resole resin may also vary widely. Suitable aldehydes include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, and benzaldehyde. In general, the aldehydes used have the formula RCHO, where R is a hydrogen or a hydrocarbon radical of 1 to 8 carbon atoms. The most preferred aldehyde is formaldehyde.
  • the basic catalysts used in preparing the phenolic resole resin include basic catalysts such as alkali or alkaline earth hydroxides, and organic amines.
  • the amount ⁇ f catalyst. Ubed will vary depending upon the specific purposes. Those skilled in the art are familiar with the levels needed.
  • the phenolic resole resins used in the practice of this invention are generally made from phenol and formaldehyde at a mole ratio of formaldehyde to phenol in the range of from about 1.1:1.0 to about 3.0:1.0.
  • the most preferred mole ratio of formaldehyde to phenol is a mole ratio in the range of from about 1.4:1.0 to about 2.2:1.0.
  • the phenolic resole resin is either formed in the aqueous basic solution, or it is diluted with an aqueous basic solution.
  • the base used in the aqueous basic solution is usually a dilute solution of an alkali or alkaline earth metal hydroxide, such as potassium hydroxide, sodium hydroxide, calcium hydroxide, or barium hydroxide, preferably potassium hydroxide or mixtures of sodium hydroxide and potassium hydroxide, in water such that the solution typically contains from about 25 to about 55 percent water by weight.
  • an alkali or alkaline earth metal hydroxide such as potassium hydroxide, sodium hydroxide, calcium hydroxide, or barium hydroxide, preferably potassium hydroxide or mixtures of sodium hydroxide and potassium hydroxide
  • aqueous basic solutions described herein are not novel products, nor is their method of preparation.
  • the parameters set forth pertaining to their preparations are merely guidelines for those who want to make the aqueous basic solutions. There may be other effective ways to make them which are not described herein.
  • the oxyanions present in the binder composition act as cross-linking agents for the resin by forming complexes with adjacent resole phenol-aldehyde chains.
  • the cross- linking action of the oxyanions is promoted by the carbon dioxide gas which is passed through the foundry shape formed with the aggregate and binder composition.
  • the exact mechanism by which the carbon dioxide promotes curing of the resin is not certain but the carbon dioxide forms carbonic acid by the reaction with water in the binder composition, thus lowering the pH of the binder.
  • the oxyanions form stable complexes with the resin molecules at the reduced pH.
  • the alkalinity of the binder composition must be such that the oxyanions remain largely in the uncomplexed state before gassing with carbon dioxide. Complexing and hence curing of the resin on the passage of carbon dioxide takes place when the pH is reduced.
  • Suitable oxyanions for use in the process and binder composition of the invention include borate, stannate and aluminate ions. Borate ions are preferred.
  • the oxyanion may be introduced into the binder composition by the addition of for example alkali metal oxyanion salts such as sodium tetraborate decahydrate, potassium tetraborate tetrahydrate, sodium metaborate, sodium bentaborate, sodium stannate trihydrate or sodium aluminaLe, or an ammonium oxyanion salt such as ammonium borate.
  • alkali metal oxyanion salts such as sodium tetraborate decahydrate, potassium tetraborate tetrahydrate, sodium metaborate, sodium bentaborate, sodium stannate trihydrate or sodium aluminaLe, or an ammonium oxyanion salt such as ammonium borate.
  • Borate ions may also be introduced by the addition of boric acid or they may be formed by reaction between boric oxide and alkali in
  • the mole ratio of oxyanions (expressed as boron, tin, etc.) to phenol is preferably in the range of from 0.1:1 to 1:1.
  • the mole ratio of boron to phenol is more preferably in the range of from 0.1:1 to 0.5:1.
  • any foundry aggregate can be used to prepare the foundry mix.
  • the aggregate will be sand which contains at least 70 percent by weight silica.
  • suitable sand includes zircon, olivine, alumina-silicate sand, chromite sand, and the like.
  • the particle size of the sand is such that at least 80 percent by weight of the sand has an average particle size between 50 and 150 mesh (Tyler Screen Mesh) . Mixtures of sand and reclaimed sand can used.
  • optional constituents can be used in the binder system.
  • a particularly useful additive to the binder compositions in certain types of sand is a silane such as those having the general formula:
  • R' is a hydrocarbon radical and preferably an alkyl radical of 1 to 6 carbon atoms and R is an alkyl radical, an alkoxy substituted alkyl radical, or an alkyl amine substituted alkyl radical in which the alkyl groups have from 1 to 6 carbon atoms.
  • silanes when employed in concentrations of 0.1% to 2%, based on the phenolic binder and hardener, improve the humidity resistance of the system.
  • silanes examples include Dow Corning Z6040 and Union Carbide A-187 (gamma glycidoxy propyltrimethoxy silane) ; Union Carbide A-1100 (gamma aminopropyltriethoxy silane); Union Carbide A-1120 (N- beta (aminoethyl)-gamma-amino-propyltrimethoxy silane); and Union Carbide A-1160 (Ureido-silane) .
  • the binders may also contain optional components such glycols, methanol, and pyrrolidone in an amount of 1-15 percent by weight based upon the weight of the resin. See for instance European Patent Applications 0 503 759 A2 where pyrrolidone is the additive, 0 508 566 A2 where a phenyl ethylene glycol ether is the additive, and U.K. Patent Application GB 2 253 627 where an aliphatic glycol ether is the additive. Amounts Of Components Used In making foundry shapes, the aggregate constitutes the major (typically more than 90 percent by weight of the total weight of the foundry shape) constituent and the binder constitutes a relatively minor amount.
  • the amount of binder which includes the resin and oxyanion, is generally no greater than about ten percent by weight and frequently within the range of about 0.5 to about 7 percent by weight based upon the weight of the aggregate. Most often, the binder content ranges from 0.6 to about 5.0 percent by weight based upon the weight of the aggregate.
  • the weight ratio of resin component to oxyanion component is from about 5:1 to about 50:1, preferably from about 10:1 to 40:1, most preferably from about 15:1 about 30:1.
  • a foundry mix is typically prepared by mixing the aqueous solution of the phenolic resole resin containing the oxyanion with the aggregate and other optional components.
  • Foundry shapes are prepared with the foundry mixes by blowing the foundry mix into a heated corebox at pressures from 0.3 to 6.0 kg/cm 2 , according to techniques well known in the art to form a foundry shape. The foundry shape is then gassed with carbon dioxide and left in the corebox until it is workable, typically from 1 second to
  • a workable foun ⁇ ry shape is one which can be handled without breaking when it is removed from the pattern. Curing with carbon dioxide is carried out according to techniques well known in the art.
  • Curing is affected by subjecting the foundry shapes to carbon dioxide gas in the presence of heat.
  • the source of heat is the corebox equipment itself.
  • the temperature of the corebox is from 30°C to 120°C, preferably
  • Heating time is a function of the temperature and the heating process used. Other sources of heat include warm air, a conventional oven, or a microwave.
  • Typical gassing times for the carbon dioxide are from 1 second to 60 seconds. Typical concentrations of carbon dioxide are 10 to 100%.
  • the foundry shape is subjected to temperatures of 30°C to 120°C , preferably from 60°C to 80°C.
  • Metal castings are produced from the workable foundry shapes in a conventional manner. Essentially, molten metal (ferrous or non-ferrous) is poured into and around the workable foundry shape and allowed to harden. The workable foundry shape is then removed.
  • the binder used in the examples was NOVANOL-100 binder which is sold by Ashland Suedchemie Kernfest.
  • NOVANOL-100 is a borate (about 4% by weight of the resin) containing phenol-formaldehyde base catalyzed resole condensate prepared by reacting phenol, paraformaldehyde, and water in the presence of dilute alkali hydroxide bases (45% to 50% in water) at increased temperatures.
  • the resin also contains glycols in the amount of about 12% by weight based upon the weight of the resin.
  • the resin component has a solids content of about 60 percent, a viscosity of about 300 centipoise at 25°C.
  • Sand Tests Foundry mixes were prepared with various two component binder systems by mixing 2.5 weight percent, based upon the weight of sand, of NOVA OL-100 with round silica ECHAVE C55 sand. Foundry shapes were made with the foundry mixes by conventional cold-box techniques.
  • the foundry mixes were prepared by first mixing the sand with the aqueous basic phenolic resole resin solution containing the oxyanion. The foundry mix was then forced into a standard core box (dog bone shape/3.5 cm 2 ) and gassed with C0 2 for 30 seconds. The scratch hardness of foundry shapes made with the binders were measured according to the Dietar Machine using standard testing procedures used for cold-box foundry binders. In all of these examples, the same components and amounts were used unless otherwise specified.
  • Tests were conducted to determine the effect of using a heated and unheated corebox on tensile strengths and scratch hardness.
  • examples designated by the A-C are controls.
  • the controls show the effect of curing the foundry shapes with carbon dioxide at room temperature.
  • Table I indicates that curing the foundry shapes the presence of heat improved the scratch hardness of the foundry shape, and that acceptable cores were made with a gassing time of 30 seconds. Improved scratch hardness is particularly important when making bulky ceres which can be roughly handled in an industrial setting, for instance those weighing up to 100 kilograms and having dimensions of from 100 X 100 X 100 cm 3 . Improvements m scratch hardness result in a better surface finish for cas t ings which reduces casting defects and machining.
  • Example 5 shows that an acceptable core can be made with a gassing time as little as 5 seconds. Shorter gassing times result in shorter cycle times.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne un procédé en boîte froide servant à préparer des formes de fonderie. Ce procédé consiste à cuire une forme de fonderie en soumettant celle-ci à du dioxyde de carbone et à la chaleur. On réalise la forme de fonderie en mélangeant un agrégat avec un liant de fonderie, lequel comprend: (a) une solution basique aqueuse d'une résine de type phénolique de type résol; et (b) de préférence, un composé qui est une source d'un oxanion. L'invention concerne également un procédé de coulée d'alliages non ferreux à l'aide de ces formes de fonderie.
PCT/US1996/018595 1995-11-21 1996-11-20 Procede en boîte froide servant a preparer des formes de fonderie WO1997018913A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10787/97A AU1078797A (en) 1995-11-21 1996-11-20 Cold-box process for preparing foundry shapes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56119095A 1995-11-21 1995-11-21
US08/561,190 1995-11-21

Publications (1)

Publication Number Publication Date
WO1997018913A1 true WO1997018913A1 (fr) 1997-05-29

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003016400A1 (fr) * 2001-07-26 2003-02-27 Ashland-Südchemie-Kernfest GmbH Systeme de liant durcissable au co2 a base de resol
EP1449602A1 (fr) * 2003-02-04 2004-08-25 General Motors Corporation Méthode de fabrication d'un moule de coulée au sable
EP2052798A1 (fr) * 2008-11-25 2009-04-29 Hüttenes-Albertus Chemische-Werke GmbH Compositions de liant en résol de phénol-aldéhyde alcaline
EP2416907A1 (fr) * 2009-04-07 2012-02-15 Ashland Licensing and Intellectual Property LLC Compositions de résine résol phénolique alcaline et leurs utilisations
CN103028703A (zh) * 2011-09-30 2013-04-10 齐齐哈尔轨道交通装备有限责任公司 二氧化碳硬化冷芯盒制芯方法及车钩钩体芯制造方法
DE102016211971A1 (de) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers
WO2018002121A1 (fr) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Composition alcaline aqueuse comme liant, à durcissement au dioxyde de carbone, son utilisation, mélange de matières moulables correspondant pour la fabrication d'un corps moulé de fonderie, corps moulé de fonderie correspondant et procédé de fabrication d'un corps moulé de fonderie

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4985489A (en) * 1987-12-24 1991-01-15 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein
US5162393A (en) * 1991-04-25 1992-11-10 Foseco International Limited Production of foundry sand moulds and cores
US5198478A (en) * 1991-03-13 1993-03-30 Foseco International Limited Alkaline resol phenol-aldehyde resin binder compositions
US5242957A (en) * 1991-03-13 1993-09-07 Foseco International Limited Alkaline resol phenol-aldehyde resin binder compositions containing phenyl ethylene glycol ether
US5294648A (en) * 1991-03-13 1994-03-15 Foseco International Limited Alkaline resol phenol-aldehyde resin binder composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4985489A (en) * 1987-12-24 1991-01-15 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein
US5198478A (en) * 1991-03-13 1993-03-30 Foseco International Limited Alkaline resol phenol-aldehyde resin binder compositions
US5242957A (en) * 1991-03-13 1993-09-07 Foseco International Limited Alkaline resol phenol-aldehyde resin binder compositions containing phenyl ethylene glycol ether
US5294648A (en) * 1991-03-13 1994-03-15 Foseco International Limited Alkaline resol phenol-aldehyde resin binder composition
US5162393A (en) * 1991-04-25 1992-11-10 Foseco International Limited Production of foundry sand moulds and cores

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003016400A1 (fr) * 2001-07-26 2003-02-27 Ashland-Südchemie-Kernfest GmbH Systeme de liant durcissable au co2 a base de resol
EP1449602A1 (fr) * 2003-02-04 2004-08-25 General Motors Corporation Méthode de fabrication d'un moule de coulée au sable
US6843303B2 (en) 2003-02-04 2005-01-18 General Motors Corporation Method of sand coremaking
US8148463B2 (en) 2008-11-25 2012-04-03 Huttenes-Albertus Chemische Werke Gmbh Alkaline resol phenol-aldehyde resin binder compositions
WO2010060826A1 (fr) * 2008-11-25 2010-06-03 Hüttenes-Albertus Chemische Werke GmbH Liants à base de résine phénol-aldéhyde de résol alcalin
EP2052798A1 (fr) * 2008-11-25 2009-04-29 Hüttenes-Albertus Chemische-Werke GmbH Compositions de liant en résol de phénol-aldéhyde alcaline
AU2009319113B2 (en) * 2008-11-25 2014-05-22 Huttenes-Albertus Chemische Werke Gmbh Alkaline resol phenol-aldehyde resin binder compositions
EP2416907A1 (fr) * 2009-04-07 2012-02-15 Ashland Licensing and Intellectual Property LLC Compositions de résine résol phénolique alcaline et leurs utilisations
EP2416907A4 (fr) * 2009-04-07 2013-10-02 Ashland Licensing & Intellectu Compositions de résine résol phénolique alcaline et leurs utilisations
CN103028703A (zh) * 2011-09-30 2013-04-10 齐齐哈尔轨道交通装备有限责任公司 二氧化碳硬化冷芯盒制芯方法及车钩钩体芯制造方法
DE102016211971A1 (de) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers
WO2018002121A1 (fr) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Composition alcaline aqueuse comme liant, à durcissement au dioxyde de carbone, son utilisation, mélange de matières moulables correspondant pour la fabrication d'un corps moulé de fonderie, corps moulé de fonderie correspondant et procédé de fabrication d'un corps moulé de fonderie
WO2018002129A1 (fr) 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Composition alcaline aqueuse de liant, à durcir avec du dioxyde de carbone, son utilisation, mélange de matières à mouler correspondant pour la fabrication d'un corps de moule de fonderie, corps de moule de fonderie correspondant et procédé de fabrication d'un corps moule de fonderie
DE102016211970A1 (de) 2016-06-30 2018-01-18 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers

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