EP0198290A2 - Method of casting aluminium alloys - Google Patents

Method of casting aluminium alloys Download PDF

Info

Publication number
EP0198290A2
EP0198290A2 EP86104247A EP86104247A EP0198290A2 EP 0198290 A2 EP0198290 A2 EP 0198290A2 EP 86104247 A EP86104247 A EP 86104247A EP 86104247 A EP86104247 A EP 86104247A EP 0198290 A2 EP0198290 A2 EP 0198290A2
Authority
EP
European Patent Office
Prior art keywords
salt mixture
wall
casting
mold
alkali
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP86104247A
Other languages
German (de)
French (fr)
Other versions
EP0198290B1 (en
EP0198290A3 (en
Inventor
Friedrich Dr.-Ing. Behr
Heinrich Dipl.-Ing. Ballewski
Wolfgang Grossmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Technologies AG
Original Assignee
Thyssen Industrie AG
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 Thyssen Industrie AG filed Critical Thyssen Industrie AG
Publication of EP0198290A2 publication Critical patent/EP0198290A2/en
Publication of EP0198290A3 publication Critical patent/EP0198290A3/en
Application granted granted Critical
Publication of EP0198290B1 publication Critical patent/EP0198290B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002Castings of light metals
    • B22D21/007Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C3/00Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor

Definitions

  • the invention relates to a method for casting aluminum alloys which contain more aluminum than the eutectic with the alloy partners, in order to achieve improved strength values by reducing the distances between the dendrite arm distances formed by solidification.
  • the technological properties of the aluminum alloys in particular the strength, the yield strength and the elongation, can be improved by fine-grain of the casting.
  • the strength properties of aluminum alloys are directly dependent on the number and fineness of the smallest possible dendrite arm distances - the secondary dendrite arm distances.
  • the fine-grained nature of aluminum and aluminum-based alloys is improved by adding a pre-alloy to the aluminum alloy before casting, which can be used as heterogeneous nuclei e.g. Contains titanium diboride.
  • the refractory material for dipping is added in the same way as in the abovementioned document as germs, noble metals or reducible metal oxides.
  • the US-PS 3 157 926 works in the same way and names nickel-III-oxide, cobalt-II-oxide and -III-oxide and nickel-cobalt oxyhydrate as seeds.
  • the seeds of the above-mentioned US patents are not effective for reducing the secondary dendrite arm spacings and thus for improving the strength properties of hypoeutectic aluminum alloys and are not proposed by the US patents. No corresponding seeds have been found for aluminum base melts, which are suitable for embedding in the mold wall to produce a fine-grained casting.
  • DE-PS 963 642 teaches to influence the surface of castings by adding additives to the molding material and alloys the surface with lead released by chemical reaction with the casting metal.
  • To avoid edge decarburization reducing protective substances are added to the molding material according to DE-AS 12 71 909, the melting point of which lies between the casting temperature and the firing temperature of the casting mold.
  • DE-AS 12 65 356 discloses to add a hydrogen-releasing metal hydride to the casting mold in its mold cavity.
  • the hydrogen is said to reduce the oxide skin of, for example, incoming iron as the casting material and thus increase the flowability.
  • the aluminum oxide of the cast skin of aluminum cannot be reduced with hydrogen.
  • the presence of hydrogen when casting aluminum alloys is also highly undesirable because gas bubbles form.
  • German writings only disclose that the surface of the casting can be influenced by means of substances introduced into the mold.
  • the problem of achieving improved fine grain, especially the reduced secondary dendrite arm Distances of hypoeutectic aluminum alloys are neither addressed, nor can it be solved with the measures mentioned therein.
  • the object is achieved in a method of the type mentioned in that the inner wall of the mold is produced with numerous roughness in the micro range, that the inner wall is provided with a thin layer of a salt mixture, the cations of the salt mixture predominantly from those of the alkali and / or alkaline earth metals and their anions consist predominantly of those of the halogens, and that the liquidus temperature of the salt mixture is set lower than the casting temperature of the aluminum alloy.
  • the transport of broken dendrite arms through the melt into central areas of the casting in addition to the growth of the fine dendritic solidification front, further improves the fine-grained interior or also areas of the mold inner wall that are not very effective, with a sufficient number of species Germs supplied.
  • the salts whose cations predominantly consist of alkali and / or alkaline earth and whose anions consist predominantly of halogens reliably bring about a reduction in the dendrite arm distances.
  • the invention can be advantageously configured as follows.
  • the invention recommends producing as many as possible, but more than 10 5 roughnesses per cm 2 of the mold inner wall, the ratio of depth to diameter or depth to gap width of cracks being greater than 1 to 3.
  • roughness in the form of pores, fracture edges, cracks and crevices, and preferably funnel-shaped depressions formed by sequences of microcrystalline fracture edges, which face the casting with the enlarging opening are recommended.
  • Geometrically particularly favorable roughnesses are e.g. obtained by arranging a ceramic material which tends to break the shell in particularly finely ground grains with a diameter of predominantly less than 10 ⁇ m on the inner wall of the mold. This happens e.g. by "dipping", i.e. Dipping the wax model in a slip on an aqueous or alcoholic basis, which also contains a binder, e.g. based on silicon dioxide. It is also possible to use other ceramic powders which have suitable pore sizes and / or a suitable fine grain because of the way in which they are produced.
  • the salt mixture contains one or more alkali and / or alkaline earth pseudohalogen compounds or else organic salts of the alkali and / or additionally contains alkaline earth metals
  • Suitable alkali or alkaline earth pseudohalogen compounds are cyanate, cyanide, rhodanite, hexa- or tetracyano compounds, amines or amides or the like, the aikalicyanides, cyanates and rhodanides chemically related compounds.
  • the removal of the oxygen residues is effective not only when cast in air, but also when cast in a vacuum at approx. 10 torr.
  • these additional salts in about 2 to 40% by weight of the total salt mixture.
  • the amount of salt added is expediently limited in such a way that the gas released during casting does not form bubbles on the surface of the casting, the released gas does not contain any molecular hydrogen and, furthermore, the salt is not stable under the pressure and temperature conditions of the preheating of the mold shell Has hydrates.
  • the inner wall and its pore entrances can be provided with different salts simultaneously and in an even, finest distribution and also apply finely ground, slurried salts that are insoluble or insufficiently soluble to the inner wall.
  • the intimate mixture of the various salts leads to rapid liquefaction.
  • the preheating of the mold which takes place before the casting, in order to improve the flow of the casting, serves at the same time to dry the applied salts. Water and / or alcohol are suitable as solvents.
  • salt mixture consisting predominantly of sodium-lithium chloride fluoride is used to coat the inner wall of the ceramic mold, the melting point of which is below 650 ° C., enables the salt mixture to be liquefied very quickly.
  • these salt mixtures there are deep-melting mixtures of reciprocal salt pairs with low hydrostability of the individual salts, especially when compared to the salts of potassium.
  • An aqueous and / or alcoholic solution of LiCl, NaF, NaC1 and Na 4 Fe (CN) 6 is particularly suitable. No premelting and grinding of the salt mixture is necessary.
  • Sodium fluoride is water soluble. Due to ion exchange with the lithium chloride, fine-grained lithium fluoride precipitates after a few hours.
  • the solution and / or slurry of the salt mixture contains a dispersing agent, fine-grained insoluble salts which separate out from the solution after some time, such as lithium fluoride, can be kept in suspension and a uniform distribution of the salt mixture on the inner wall of the mold can be promoted.
  • Suitable dispersants are e.g. Methyl cellulose.
  • Exemplary Embodiment 1 20 wax grapes were produced, each composed of eight tensile specimen models with an 8 mm diameter, the tensile specimens being arranged in a circle around a sprue and each having an annular top and bottom cut.
  • the wax grapes were given a first coating by dipping into a slurry, consisting of an aqueous binder, finely ground zirconium silicate and silicon dioxide as filler, and sanded with coarse zirconium silicate powder. After drying, a further six layers were applied by dipping, sanding and drying in a conventional manner, so that ceramic shapes with wall thicknesses of approximately 8 mm were formed.
  • the molds were waxed under pressure in an autoclave and then fired at approx. 800 ° C.
  • the solution was poured into the ceramic molds one after the other, immediately poured out again and filtered in order to remove any ceramic granules that had been rinsed out.
  • the ceramic molds were then heated to approx. 470 ° C, inserted into the vacuum casting machine when warm and at approx. 250 ° C mold temperature with the aluminum alloy GAISi7Mg0.6 at a melt temperature of 700 ° C, at 10-2 Torr filled.
  • the aluminum melt was premelted in air, then degassed with a flushing gas mixture and then degassed in vacuo.
  • the wax models of an aircraft structural part with an average wall thickness of 5 mm and at the nodes with a wall thickness of 15 mm were assembled into wax grapes according to the method described in exemplary embodiment 1, covered with the ceramic shell, waxed under pressure in the autoclave and then at approx. Fired at 800 ° C.
  • the solution was poured into the ceramic molds one after the other, immediately poured out again and filtered in order to remove any ceramic granules that had been rinsed out.
  • the ceramic molds were then heated to approx. 470 ° C, inserted into the vacuum casting machine when hot and at approx. 250 ° C mold temperature with the aluminum alloy GAISi7Mg0.6 at a melt temperature of 700 ° C, at 10 -2 Torr filled.
  • the aluminum melt was premelted in air, then degassed with a purging gas mixture and subsequently degassed in vacuo.

Abstract

1. Method for casting aluminum alloys which contain more aluminium than corresponds to the eutectic mixture with the alloy partners to achieve improved strength values by reducing the spacings of the secondary dendrite arm spacings formed by solidification, characterized in that the inner wall of the casting mould is produced with large numbers of roughnesses in the micro-range, in that the inner wall is provided with a thin layer of a salt mixture, the cations of the salt mixture consisting predominantly of those of the alkali and/or alkaline-earth metals and its anions consisting prominently of those of the halogens, and in that the liquidus temperature of the salt mixture is set lower than the casting temperature of the aluminium alloy.

Description

Die Erfindung betrifft ein Verfahren zum Vergießen von Aluminium-Legierungen, die mehr Aluminium enthalten, als dem Eutektikum mit den Legierungspartnern entspricht, zur Erzielung verbesserter Festigkeitswerte durch Verringerung der Abstände der sekundär durch Erstarrung gebildeten Dendritenarmabstände.The invention relates to a method for casting aluminum alloys which contain more aluminum than the eutectic with the alloy partners, in order to achieve improved strength values by reducing the distances between the dendrite arm distances formed by solidification.

Es ist bekannt, daß man die technologischen Eigenschaften der Aluminium-Legierungen, insbesondere die Festigkeit, die Streckgrenze und die Dehnung durch Feinkörnigkeit des Gußstückes verbessern kann. Bekanntlich sind die Festigkeitseigenschaften bei Aluminium-Legierungen direkt abhängig von der Zahl und der Feinheit der möglichst kleinen Dendritenarmabstände - den sekundären Dendritenarmabständen. Nach Foundry, Juni 1963, S. 78 - 82, wird die Feinkörnigkeit von Aluminium- und Aluminium-Basis-Legierungen dadurch verbessert, daß in die Aluminium-Legierung vor dem Abguß eine Vorlegierung zugefügt wird, die als heterogene Keime z.B. Titan-Diborid enthält.It is known that the technological properties of the aluminum alloys, in particular the strength, the yield strength and the elongation, can be improved by fine-grain of the casting. As is well known, the strength properties of aluminum alloys are directly dependent on the number and fineness of the smallest possible dendrite arm distances - the secondary dendrite arm distances. According to Foundry, June 1963, pp. 78 - 82, the fine-grained nature of aluminum and aluminum-based alloys is improved by adding a pre-alloy to the aluminum alloy before casting, which can be used as heterogeneous nuclei e.g. Contains titanium diboride.

Aus der US-PS 3 259 948 ist es bekannt, die Feinkörnigkeit von Gußstücken aus Kobalt- oder Nickel-Basis-Legierungen durch Einbringen von Keimen in die innere Gießformoberfläche zu verbessern. Diese Keine, z.B. Kobaltaluminat und Kobaltsilikat werden nach der US-PS auf das Wachsmodell aufgetragen und durch das anschließende Eintauchen des Wachsmodelles in einen Schlicker aus feuerfestem Formmaterial und Ausschmelzen des Wachsmodelles zum Teil in die innere Formoberfläche eingebettet (Dippen). Nach der US-PS 3 019 497 werden, ebenfalls zum Zwecke der Kornverfeinerung, Keime mit dem Feuerfestmaterial für das Dippen gemischt und auf das Wachsmodell aufgetragen. Nach der US-PS 3 158 912 werden dem Feuerfestmaterial für das Dippen in gleicher Weise wie in der eben genannten Schrift als Keime, Edelmetalle oder reduzierbare Metalloxyde beigefügt. Die US-PS 3 157 926 arbeitet in gleicher Weise und nennt Nickel-III-Oxyd, Kobalt-II-Oxyd und -III-Oxyd und Nickel-Kobaltoxy-hydrat als Keime. Die Keime der genannten US-Patentschriften sind für die Verringerung der sekundären Dendritenarmabstände und damit zur Verbesserung der Festigkeitseigenschaften von untereutektischen Aluminium-Legierungen nicht wirksam und werden von den US-Patentschriften nicht vorgeschlagen. Für Aluminium-Basisschmelzen sind noch keine entsprechenden Keime, die sich zur Einbettung in die Formwand zur Erzeugung eines feinkörnigen Gußstücks eignen, gefunden worden. Nach Foundry 1963 wird die Feinkörnigkeit von Aluminium-Legierungen durch Zugabe der Keime mit der Vorlegierung verbessert. Dies ist jedoch bezüglich der Zuverlässigkeit und des möglichst geringen sekundären Dendritenarmabstandes unbefriedigend. Die DE-PS 963 642 lehrt, die Oberfläche von Gußkörpern durch Zusätze zum Formwerkstoff zu beeinflussen und legiert die Oberfläche mit durch chemische Reaktion mit dem Gießmetall freigesetzten Blei. Zur Vermeidung der Randentkohlung werden nach der DE-AS 12 71 909 dem Formstoff reduzierende Schutzstoffe zugesetzt, deren Schmelzpunkt zwischen der Gießtemperatur und der Brenntemperatur der Gießform liegt. Die DE-AS 12 65 356 offenbart, die Gießform in ihrem Formhohlraum mit einem Wasserstoff freisetzenden Metallhydrid zu versetzen. Der Wasserstoff soll die Oxydhaut von z.B. einlaufendem Eisen als Gießmaterial reduzieren und damit die Fließfähigkeit erhöhen. Bekanntlich ist das Aluminiumoxyd der Gußhaut von Aluminium nicht mit Wasserstoff reduzierbar. Die Gegenwart von Wasserstoff beim Abguß von Aluminium-Legierungen ist zudem in höchstem Maße unerwünscht, da Gasblasenbildung einsetzt.From US Pat. No. 3,259,948 it is known to improve the fine-grain nature of castings made of cobalt or nickel-based alloys by introducing germs into the inner mold surface. These none, for example cobalt aluminate and cobalt silicate, are applied to the wax model in accordance with the US Pat. And by subsequently immersing the wax model in a slip made of refractory molding material and melting out the Wax models partially embedded in the inner mold surface (dipping). According to US Pat. No. 3,019,497, germs are also mixed with the refractory material for dipping and applied to the wax model, likewise for the purpose of grain refinement. According to US Pat. No. 3,158,912, the refractory material for dipping is added in the same way as in the abovementioned document as germs, noble metals or reducible metal oxides. The US-PS 3 157 926 works in the same way and names nickel-III-oxide, cobalt-II-oxide and -III-oxide and nickel-cobalt oxyhydrate as seeds. The seeds of the above-mentioned US patents are not effective for reducing the secondary dendrite arm spacings and thus for improving the strength properties of hypoeutectic aluminum alloys and are not proposed by the US patents. No corresponding seeds have been found for aluminum base melts, which are suitable for embedding in the mold wall to produce a fine-grained casting. According to Foundry 1963, the fine grain of aluminum alloys is improved by adding the germs with the master alloy. However, this is unsatisfactory in terms of reliability and the smallest possible secondary dendrite arm spacing. DE-PS 963 642 teaches to influence the surface of castings by adding additives to the molding material and alloys the surface with lead released by chemical reaction with the casting metal. To avoid edge decarburization reducing protective substances are added to the molding material according to DE-AS 12 71 909, the melting point of which lies between the casting temperature and the firing temperature of the casting mold. DE-AS 12 65 356 discloses to add a hydrogen-releasing metal hydride to the casting mold in its mold cavity. The hydrogen is said to reduce the oxide skin of, for example, incoming iron as the casting material and thus increase the flowability. As is known, the aluminum oxide of the cast skin of aluminum cannot be reduced with hydrogen. The presence of hydrogen when casting aluminum alloys is also highly undesirable because gas bubbles form.

Die deutschen aenannten Schriften offenbaren lediglich, daß man das Gußstück mit Hilfe von in die Form eingebrachten Stoffen an seiner Oberfläche beeinflussen kann. Das Problem der Erzielung einer verbesserten Feinkörnigkeit, insbesondere der verringerten sekundären Dendritenarmabstände untereutektischer Aluminium-Legierungen wird dabei weder anqesprochen, noch ist es mit den darin genannten Maßnahmen lösbar.The so-called German writings only disclose that the surface of the casting can be influenced by means of substances introduced into the mold. The problem of achieving improved fine grain, especially the reduced secondary dendrite arm Distances of hypoeutectic aluminum alloys are neither addressed, nor can it be solved with the measures mentioned therein.

Es ist Aufgabe der Erfindung, die Feinkörnigkeit von Aluminium-Legierungen und insbesondere auch die Zuverlässigkeit bei deren Einstellung wesentlich zu verbessern.It is an object of the invention to significantly improve the fine-grained nature of aluminum alloys and, in particular, the reliability of their adjustment.

Die Aufgabe wird bei einem Verfahren der eingangs genannten Gattung dadurch gelöst, daß die Innenwand der Gießform mit zahlreichen Rauhigkeiten im Mikrobereich hergestellt wird, daß die Innenwand mit einer dünnen Schicht einer Salzmischung versehen wird, wobei die Kationen der Salzmischung überwiegend aus denen der Alkali- und/oder Erdalkali-Metalle bestehen und deren Anionen überwiegend aus denen der Halogene bestehen, und daß die Liquidustemperatur der Salzmischung tiefer eingestellt wird als die Abgußtemperatur der Aluminium-Legierung.The object is achieved in a method of the type mentioned in that the inner wall of the mold is produced with numerous roughness in the micro range, that the inner wall is provided with a thin layer of a salt mixture, the cations of the salt mixture predominantly from those of the alkali and / or alkaline earth metals and their anions consist predominantly of those of the halogens, and that the liquidus temperature of the salt mixture is set lower than the casting temperature of the aluminum alloy.

Mit diesem Verfahren wurden gegenüber den bekannten Verfahren wesentlich höhere Festigkeits- und Dehnungswerte erreicht. Dies ist nach Ansicht der Anmelderin darauf zurückzuführen, daß bei den erfindungsgemä-βen Verfahren die Metallschmelze mit Hilfe der Salzmischung, die nach Abguß der Metallschmelze möglichst dünnflüssig sein sollte, auch feinste Poren und andere Rauhigkeiten der Formschalen-Innenwand auffüllt. Das Metall kühlt dort zuerst ab und erstarrt, so daß viele Kristallisationszentren in der schon auf Grund der durch die Geometrie der Formschale vorgegebenen Richtung der Wärmeabfuhr in einer kristallin günstigen Ausrichtung mit dem noch flüssigen Gußstück in Verbindung stehen und als arteigener Keim wirksam werden können. Darüber hinaus wird wohl auch durch Transport von abgebrochenen Dendritenarmen durch die Schmelze in zentrale Bereiche des Gußstückes hinein zusätzlich zu dem Heranwachsen der feinen dendritischen Erstarrungsfront die Feinkörnigkeit im Inneren noch weiter verbessert oder auch Bereiche der Forminnenwand, die wenig wirksam sind, mit einer genügenden Anzahl arteigener Keime versorgt. Dadurch, daß die keramische Form mit den Rauhigkeiten und Poren nach dem Trocknen und Brennen mit der dünnen Salzschicht versehen wird, deren Liquidustemperatur geringer ist als die Abgußtemperatur der Legierung, <ann sich die Salzmischung als dünne, filmartige Schicht, die sich bei Fingießen der Legierung verflüssigt, qleichmäßig auch in die Vertiefun- qen der Rauhigkeiten hinein ausbreiten und hindert wegen der dünnen Schicht das eingegossene Aluminium auch nicht am Eindringen in die Poren. Die Salze, deren Kationen überwiegend aus Alkali und/oder Erdalkali und deren Anionen überwiegend aus Halogenen bestehen, bewirken nach Versuchen der Anmelderin zuverlässig eine Verringerung der Dendritenarmabstände.With this method, significantly higher strength and elongation values were achieved compared to the known methods. In the view of the applicant, this can be attributed to the fact that, in the processes according to the invention, the metal melt fills even the finest pores and other roughnesses of the inner shell of the mold with the aid of the salt mixture, which should be as thin as possible after the metal melt has been poured off. The metal cools there first and solidifies, so that many crystallization centers in the direction of heat dissipation, which is already predetermined by the geometry of the molded shell, are in a crystalline favorable orientation in connection with the still liquid casting and can act as a native germ. In addition, the transport of broken dendrite arms through the melt into central areas of the casting, in addition to the growth of the fine dendritic solidification front, further improves the fine-grained interior or also areas of the mold inner wall that are not very effective, with a sufficient number of species Germs supplied. The fact that the ceramic form with the roughness and pores after drying and firing is provided with the thin salt layer, the liquidus temperature of which is lower than the casting temperature of the alloy, the salt mixture as a thin, film-like layer, which forms Fingießen the alloy liquefied, q of the asperities moderately facilitated also in the depressions into q en spread and prevents because of the thin layer of the cast aluminum not penetrating into the pores. According to the applicant's attempts, the salts whose cations predominantly consist of alkali and / or alkaline earth and whose anions consist predominantly of halogens reliably bring about a reduction in the dendrite arm distances.

Im einzelnen kann die Erfindung wie folgt vorteilhaft ausgestaltet sein.In particular, the invention can be advantageously configured as follows.

Man benötigt für die Erzielung eines möglichst geringen Unterkühlungsintervalles der Erstarrung beim Aluminium-Guß Kristallisationszentren mit Durchmessern in der Größenordnung von zehn bis einigen hundert Angström, so daß der Geometrie der Rauhigkeiten eine besondere Bedeutung zukommt. Dazu empfiehlt die Erfindung, möglichst viele, aber mehr als 105 Rauhigkeiten pro cm2 der Forminnenwand herzustellen, deren Verhältnis Tiefe zu Durchmesser oder Tiefe zu Spaltbreite von Rissen größer als 1 zu 3 ist. Fs empfehlen sich Rauhigkeiten in Form von Poren, Bruchkanten, Rissen und Spalten sowie vorzugsweise von Folgen mikrokristalliner Bruchkanten aebildete, trichterförmige Vertiefungen, die dem Gußstück mit der sich vergrößernden öffnung zugewandt sind.Crystallization centers with diameters in the order of ten to a few hundred angstroms are required to achieve the lowest possible cooling interval for solidification in aluminum casting, so that the geometry of the roughness is of particular importance. For this purpose, the invention recommends producing as many as possible, but more than 10 5 roughnesses per cm 2 of the mold inner wall, the ratio of depth to diameter or depth to gap width of cracks being greater than 1 to 3. In this case, roughness in the form of pores, fracture edges, cracks and crevices, and preferably funnel-shaped depressions formed by sequences of microcrystalline fracture edges, which face the casting with the enlarging opening, are recommended.

Geometrisch besonders günstige Rauhigkeiten werden z.B. erhalten, indem man ein keramisches Material, welches zum Muschelbruch neigt, in besonders feingemahlenen Körnungen mit überwiegend weniger als 10 pm Durchmesser an der Formeninnenwand anordnet. Das geschieht z.B. durch "Dippen", d.h. Tauchen des Wachsmodelles in einem Schlicker auf wässriger oder alkoholischer Basis, der auch einen Binder, z.B. auf Basis von Siliciumdioxyd, enthält. Es können auch andere keramische Pulver benutzt werden, die schon auf Grund ihres Herstellungsweges geeignete Porengrößen und/oder eine geeignete Feinkörnigkeit aufweisen.Geometrically particularly favorable roughnesses are e.g. obtained by arranging a ceramic material which tends to break the shell in particularly finely ground grains with a diameter of predominantly less than 10 μm on the inner wall of the mold. This happens e.g. by "dipping", i.e. Dipping the wax model in a slip on an aqueous or alcoholic basis, which also contains a binder, e.g. based on silicon dioxide. It is also possible to use other ceramic powders which have suitable pore sizes and / or a suitable fine grain because of the way in which they are produced.

Dadurch, daß die Salzmischung eine oder mehrere Alkali- und/oder Erdalkali-Pseudohalogenverbindungen oder auch organische Salze der Alkali-und/oder Erdalkali-Metalle zusätzlich enthält, kann eine verbesserte Entfernung von Sauerstoffresten, insbesondere in den Poren der Form erreicht werden. Als Alkali- oder Erdalkali-Pseudohalogenverbindungen eignen sich Cyanat-, Cyanid-, Rhodanit-, Hexa- oder Tetracyano-Verbindungen, Amine oder Amide o.ä., den Aikalicyaniden, -cyanaten und -rhodaniden chemisch verwandte Verbindungen. Die Entfernung der Sauerstoffreste ist nicht nur bei Abguß an Luft wirksam, sondern auch bei Abguß im Vakuum bei ca. 10 Torr. Dabei ist es vorteilhaft, diese zusätzlichen Salze in etwa 2 - 40 Gew.% der Gesamtsalzmischung zuzugeben. Zweckmäßig wird der Salzzusatz in seiner Menge so begrenzt, daß es durch beim Abguß freiqesetztes Gas nicht zur Bildung von Blasen an der Gußstückoberfläche kommt, das freiqesetzte Gas keinen molekularen Wasserstoff enthält und weiterhin das Salz bei den Druck- und Temperaturbedingungen der Vorwärmung der Formschale keine stabilen Hydrate aufweist.The fact that the salt mixture contains one or more alkali and / or alkaline earth pseudohalogen compounds or else organic salts of the alkali and / or additionally contains alkaline earth metals, an improved removal of oxygen residues, in particular in the pores of the mold, can be achieved. Suitable alkali or alkaline earth pseudohalogen compounds are cyanate, cyanide, rhodanite, hexa- or tetracyano compounds, amines or amides or the like, the aikalicyanides, cyanates and rhodanides chemically related compounds. The removal of the oxygen residues is effective not only when cast in air, but also when cast in a vacuum at approx. 10 torr. It is advantageous to add these additional salts in about 2 to 40% by weight of the total salt mixture. The amount of salt added is expediently limited in such a way that the gas released during casting does not form bubbles on the surface of the casting, the released gas does not contain any molecular hydrogen and, furthermore, the salt is not stable under the pressure and temperature conditions of the preheating of the mold shell Has hydrates.

Dadurch, daß die Salzmischung in Form einer Lösung und/oder feindisperser Aufschlämmung durch Ein- und Ausgießen in die gebrannte Form auf deren Innenwand mit anschließender Trocknung aufgebracht wird, kann man die Innenwand und deren Poreneingänge mit verschiedenen Salzen gleichzeitig und in gleichmäßiger, feinster Verteilung versehen und außerdem feinstqemahlene, aufgeschlämmte Salze, die nicht löslich oder zu wenig löslich sind, auf die Innenwand aufbringen. Bei der Abgußtemperatur führt die innige Mischung der verschiedenen Salze zu einer schnellen Verflüssigung. Die Vorwärmung der Form, die vor dem Abguß erfolgt, um das Auslaufen des Gußstückes zu verbessern, dient dabei gleichzeitig zum Trocknen der aufgebrachten Salze. Als Lösungsmittel eignen sich Wasser und/oder Alkohol.Because the salt mixture in the form of a solution and / or finely dispersed slurry is applied to the inner wall by subsequent pouring and pouring into the fired mold with subsequent drying, the inner wall and its pore entrances can be provided with different salts simultaneously and in an even, finest distribution and also apply finely ground, slurried salts that are insoluble or insufficiently soluble to the inner wall. At the pouring temperature, the intimate mixture of the various salts leads to rapid liquefaction. The preheating of the mold, which takes place before the casting, in order to improve the flow of the casting, serves at the same time to dry the applied salts. Water and / or alcohol are suitable as solvents.

Dadurch, daß eine überwiegend aus Natrium-Lithium-Chlorid-Fluorid bestehende Salzmischung zur Beschichtung der Innenwand der keramischen Form verwendet wird, deren Schmelzpunkt unterhalb von 650°C liegt, kann eine sehr schnelle Verflüssigung des Salzgemisches erreicht werden. Bei diesen Salzgemischen existieren tiefschmelzende Mischungen reziproker Salzpaare mit geringer Hydrostabilität der Einzelsalze, insbesondere verglichen mit den Salzen des Kaliums.The fact that a salt mixture consisting predominantly of sodium-lithium chloride fluoride is used to coat the inner wall of the ceramic mold, the melting point of which is below 650 ° C., enables the salt mixture to be liquefied very quickly. In these salt mixtures, there are deep-melting mixtures of reciprocal salt pairs with low hydrostability of the individual salts, especially when compared to the salts of potassium.

Besonders geeignet ist eine wässrige und/oder alkoholische Lösung aus LiCl, NaF, NaC1 und Na4Fe (CN)6. Dabei ist kein Vorschmelzen und Mahlen der Salzmischung notwendig. Natriumfluorid ist wasserlöslich. Durch Ionenaustausch mit dem Lithium-Chlorid fällt nach einigen Stunden feinkörniges Lithiumfluorid aus.An aqueous and / or alcoholic solution of LiCl, NaF, NaC1 and Na 4 Fe (CN) 6 is particularly suitable. No premelting and grinding of the salt mixture is necessary. Sodium fluoride is water soluble. Due to ion exchange with the lithium chloride, fine-grained lithium fluoride precipitates after a few hours.

Dadurch, daß die Lösung und/oder Aufschlämmung des Salzgemisches ein Dispergiermittel enthält, können feinkörnige unlösliche Salze, die sich nach einiger Zeit aus der Lösung ausscheiden wie das Lithiumfluorid, in der Schwebe gehalten werden und eine gleichmäßige Verteilung der Salzmischung auf der Forminnenwand gefördert werden. Als Dispergiermittel eignet sich z.B. Methyl-Zellulose.Because the solution and / or slurry of the salt mixture contains a dispersing agent, fine-grained insoluble salts which separate out from the solution after some time, such as lithium fluoride, can be kept in suspension and a uniform distribution of the salt mixture on the inner wall of the mold can be promoted. Suitable dispersants are e.g. Methyl cellulose.

Fördernd für die qleichmäßige Verteilung des Salzgemisches bei der Trocknung wirkt auch, daß der Lösung und/oder der Aufschlämmung des Salzgemisches ein die Benetzung der Innenwand der keramischen Form verbesserndes Hilfsmittel wie ein Tensid zugegeben wird.The fact that the solution and / or the slurry of the salt mixture is admixed with an auxiliary agent which improves the wetting of the inner wall of the ceramic mold, such as a surfactant, also promotes the uniform distribution of the salt mixture during drying.

Im folgenden wird die Erfindung anhand von Ausführungsbeispielen erläutert.The invention is explained below using exemplary embodiments.

Die Untersuchungen ergaben, daß die senkundären Dendritenarmabstände etwa 40 - 50 um betrugen, während bei nach dem Stand der Technik mit einer Titandiborid-Vorlegierung versetztem Material solche von ca. 80 - 90 pm unter gleichen Gießbedingungen gefunden wurden.The investigations showed that the secondary dendrite arm distances were approximately 40-50 μm, while those of the prior art with a titanium diboride master alloy were found to have approximately 80-90 μm under the same casting conditions.

Ausführungsbeispiel 1 Es wurden 20 Wachstrauben hergestellt, die aus je acht Zugproben-Modellen mit 8 mm Durchmesser zusammengesetzt waren, wobei die Zugproben um einen Einguß kreisförmig angeordnet und mit je einem ringförmigen Ober-und Unteranschnitt versehen waren.Exemplary Embodiment 1 20 wax grapes were produced, each composed of eight tensile specimen models with an 8 mm diameter, the tensile specimens being arranged in a circle around a sprue and each having an annular top and bottom cut.

Die Wachstrauben wurden mit einem ersten überzug durch Tauchen in eine Aufschlämmung, bestehend aus einem wässrigen Binder, feingemahlenem 30 µm) Zirkonsilikat und Siliziumdioxyd als Füller, versehen und mit grobem Zirkonsilikatpulver besandet. Nach der Trocknung wurden weitere sechs Schichten durch Tauchen, Besanden und Trocknen in üblicher Weise aufgebracht, so daß keramische Formen mit Wandstärken von ca. 8 mm entstanden. Die Formen wurden unter Druck im Autoklaven entwachst und anschließend bei ca. 800°C gebrannt.The wax grapes were given a first coating by dipping into a slurry, consisting of an aqueous binder, finely ground zirconium silicate and silicon dioxide as filler, and sanded with coarse zirconium silicate powder. After drying, a further six layers were applied by dipping, sanding and drying in a conventional manner, so that ceramic shapes with wall thicknesses of approximately 8 mm were formed. The molds were waxed under pressure in an autoclave and then fired at approx. 800 ° C.

Es wurde weiterhin eine wässrige Lösung aus 20 g LiCl, 20 g NaF, 5 g Na4Fe (CN)6, 40 g NaCl, 1 g Methylzellulose und 0,1 g Tensid pro Liter angesetzt.An aqueous solution of 20 g LiCl, 20 g NaF, 5 g Na 4 Fe (CN) 6 , 40 g NaCl, 1 g methyl cellulose and 0.1 g surfactant per liter was also prepared.

Die Lösung wurde nacheinander in die keramischen Formen gefüllt, sofort wieder ausgegossen und filtriert, um ggf. ausgespülte Keramikkörner zu entfernen.The solution was poured into the ceramic molds one after the other, immediately poured out again and filtered in order to remove any ceramic granules that had been rinsed out.

Die keramischen Formen wurden dann auf ca. 470°C erhitzt, im warmen Zustand in die Vakuumgießanlage eingesetzt und bei ca. 250°C Formtemperatur mit der Aluminium-Legierung GAISi7Mg0.6 bei einer Temperatur der Schmelze von 700°C, bei 10-2 Torr gefüllt.The ceramic molds were then heated to approx. 470 ° C, inserted into the vacuum casting machine when warm and at approx. 250 ° C mold temperature with the aluminum alloy GAISi7Mg0.6 at a melt temperature of 700 ° C, at 10-2 Torr filled.

Die Aluminium-Schmelze wurde an Luft vorgeschmolzen, dann durch ein Spülgasgemisch entgast und im Vakuum nachentgast.The aluminum melt was premelted in air, then degassed with a flushing gas mixture and then degassed in vacuo.

Nach der üblichen Wärmebehandlung, die Lösungsglühen und Aushärten umfaßte, wurden folgende Festigkeitswerte bei geringer Streuung erhalten.

  • Zugfestigkeit Rm > 340 N/mm2
  • Streckgrenze Rp0.2 > 280 N/mm 2
  • Bruchdehnung A5 > 6.5 %
After the usual heat treatment, which included solution annealing and hardening, the following strength values were obtained with little scatter.
  • Tensile strength R m > 340 N / mm 2
  • Yield strength R p0.2 > 280 N / mm 2
  • Elongation at break A 5 > 6.5%

Ausführungsbeispiel 2Embodiment 2

Es wurden die Wachsmodelle eines Flugzeugstrukturteiles mit einer mittleren Wandstärke von 5 mm und an den Knotenpunkten mit einer Wandstärke von 15 mm nach der in Ausführungsbeispiel 1 beschriebenen Methode zu Wachstrauben zusammengestellt, mit der keramischen Schale überzogen, im Autoklaven unter Druck entwachst und anschließend bei ca. 800°C gebrannt.The wax models of an aircraft structural part with an average wall thickness of 5 mm and at the nodes with a wall thickness of 15 mm were assembled into wax grapes according to the method described in exemplary embodiment 1, covered with the ceramic shell, waxed under pressure in the autoclave and then at approx. Fired at 800 ° C.

Es wurde weiterhin eine wässrige Lösung aus 20 g LiCl, 20 g NaF, 5 g Na4Fe (CN)6, 40 g NaCl, 1 g Methylzellulose und 0,1 g Tensid pro Liter angesetzt.An aqueous solution of 20 g LiCl, 20 g NaF, 5 g Na 4 Fe (CN) 6 , 40 g NaCl, 1 g methyl cellulose and 0.1 g surfactant per liter was also prepared.

Die Lösung wurde nacheinander in die keramischen Formen gefüllt, sofort wieder ausgegossen und filtriert, um ggf. ausgespülte Keramikkörner zu entfernen.The solution was poured into the ceramic molds one after the other, immediately poured out again and filtered in order to remove any ceramic granules that had been rinsed out.

Die keramischen Formen wurden dann auf ca. 470°C erhitzt, im warmen Zustand in die Vakuumgießanlage eingesetzt und bei ca. 250°C Formtemperatur mit der Aluminium-Legierung GAISi7Mg0,6 bei einer Temperatur der Schmelze von 700°C, bei 10-2 Torr gefüllt.The ceramic molds were then heated to approx. 470 ° C, inserted into the vacuum casting machine when hot and at approx. 250 ° C mold temperature with the aluminum alloy GAISi7Mg0.6 at a melt temperature of 700 ° C, at 10 -2 Torr filled.

Die Aluminiumschmelze wurde an Luft vorgeschmolzen, dann durch ein Spülgasgemisch entgast und im Vakuum nachentgast.The aluminum melt was premelted in air, then degassed with a purging gas mixture and subsequently degassed in vacuo.

Nach der Wärmebehandlung, die Lösungsglühen und Aushärten umfaßte, wurden folgende Festigkeitswerte bei geringer Streuung an Flachproben aus dem Feingußteil erhalten:

  • Zugfestigkeit Rm 350 bis 360 N/mm2
  • Streckgrenze Rp0.2 290 bis 310 N/mm2
  • Bruchdehnung A5 5 bis 7 %
After the heat treatment, which included solution annealing and hardening, the following strength values were obtained with little scatter on flat samples from the investment casting:
  • Tensile strength R m 350 to 360 N / mm 2
  • Yield strength R p0.2 290 to 310 N / mm 2
  • Elongation at break A 5 5 to 7%

Beim Gießen derselben Schmelze in eine bekannte Form ohne die erfindungsgemäßen Maßnahmen ergaben sich folgende Werte

  • Zugfestigekeit Rm 300 N/mm2
  • Streckgrenze Rp0.2 200 N/mm 2
  • Bruchdehnung A5 3 %
When the same melt was poured into a known mold without the measures according to the invention, the following values resulted
  • Tensile strength R m 300 N / mm 2
  • Yield strength R p0.2 200 N / mm 2
  • Elongation at break A 5 3%

Die technologischen Werte Zugfestigkeit, Streckgrenze und Bruchdehnung wurden durch den Einsatz der Erfindung somit wesentlich verbessert.The technological values of tensile strength, yield strength and elongation at break were thus significantly improved by using the invention.

Claims (9)

1. Verfahren zum Vergießen von Aluminium-Legierungen, die mehr Aluminium enthalten, als dem Entektikum mit den Legierungspartnern entspricht, zur Erzielung verbesserter Festigkeitswerte durch Verringerung der Abstände der sekundär durch Erstarrung gebildeten Dendritenarmabstände, dadurch qekennzeichnet,
daß die Innenwand der Gießform mit zahlreichen Rauigkeiten im Mikrobereich hergestellt wird,
daß die Innenwand mit einer dünnen Schicht einer Salzmischung versehen wird, wobei die Kationen der Salzmischung überwiegend aus denen der Alkali- und/oder Erdalkali-Metalle bestehen und deren Anionen überwiegend aus denen der Halogene bestehen
und daß die Liquidustemperatrur der Salzmischung tiefer eingestellt wird als die Abgußtemperatur der Aluminium-Legierung.
1. A process for casting aluminum alloys which contain more aluminum than the de-tectic with the alloy partners corresponds to in order to achieve improved strength values by reducing the distances between the dendrite arm distances formed by solidification, characterized by,
that the inner wall of the mold is produced with numerous roughness in the micro range,
that the inner wall is provided with a thin layer of a salt mixture, the cations of the salt mixture consisting predominantly of those of the alkali and / or alkaline earth metals and their anions consisting predominantly of those of the halogens
and that the liquidus temperature of the salt mixture is set lower than the casting temperature of the aluminum alloy.
?. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Innenwand der Gießform mehr als 105 Rauhigkeiten pro cm2 aufweist, deren Verhältnis von Tiefe zu Durchmesser oder Tiefe zu Spaltbreite mehr als 1 zu 3beträgt.? Method according to Claim 1, characterized in that the inner wall of the casting mold has more than 10 5 roughnesses per cm 2 , the ratio of depth to diameter or depth to gap width being more than 1 to 3. 3. Verfahren nach Anspruch 2, dadurch qekennzeichnet, daß das die Innenwand der Gießform bildende Feuerfestmaterial aus feinstkörnigen, durch Mahlen gewonennen Oxydpulvern durch Eintauchen eines Wachsmodelles in eine Aufschlämmung aus dem Oxydpulver, einem Füller und einem Binder, Trocknen und Brennen unter Bildung einer oxydkeramischen Bindung durch den Binder hergestellt wird.3. The method according to claim 2, characterized in that the refractory material which forms the inner wall of the casting mold and consists of very fine-grained oxide powders obtained by grinding by immersing a wax model in a slurry of the oxide powder, a filler and a binder, drying and firing to form an oxide-ceramic bond is produced by the binder. 1. Verfahren nach einem der obigen Ansprüche, dadurch gekennzeichnet, daß die verwendete Salzmischung zusätzlich eine oder mehrere Alkali-und/oder Erdalkali-Pseudohalogenverbindungen in Form von Cyanat-, Cyanid-, Rhodanid-, Hexa- und/oder Tetracyanoverbindungen, Aminen oder Amiden und/oder ähnlichen, den Alkalicyaniden, -Cyanaten und -Rhodaniden chemisch verwandten Verbindungen und/oder organische Salze und/oder metallorganische Verbindungen der Alkali- und/oder Erdalkalimetalle zusätzlich enthält.1. The method according to any one of the above claims, characterized in that the salt mixture used additionally one or more alkali and / or alkaline earth pseudohalogen compounds in the form of cyanate, cyanide, rhodanide, hexa- and / or tetracyano compounds, amines or amides and / or similar compounds containing the alkali metal cyanides, cyanates and rhodanides and / or organic salts and / or organometallic compounds of the alkali and / or alkaline earth metals. 5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß eine überwiegend aus Natrium-Lithium-Chlorid-Fluorid bestehende Salzmischung zur Beschichtung der Innenwand der keramischen Form verwendet wird, deren Schmelzpunkt unterhalb von 650°C liegt.5. The method according to any one of the preceding claims, characterized in that a salt mixture consisting predominantly of sodium lithium chloride fluoride is used for coating the inner wall of the ceramic mold, the melting point of which is below 650 ° C. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine wässrige und/oder alkoholische Lösung aus LiC1, NaF, NaCl und Na4Fe (CN)6 verwendet wird.6. The method according to claim 5, characterized in that an aqueous and / or alcoholic solution of LiC1, NaF, NaCl and Na 4 Fe (CN) 6 is used. 7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch qekennzeichnet, daß die Salzmischung in Form der Lösung und/oder einer feindispersen Aufschlämmung durch Ein- und Ausgießen in die gebrannte Form auf deren Innenwand und sich anschließende Trocknung aufgebracht wird.7. The method according to any one of the preceding claims, characterized in that the salt mixture in the form of the solution and / or a finely dispersed slurry is applied by pouring and pouring into the fired form on the inner wall and subsequent drying. 8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Lösung und/oder Aufschlämmung des Salzgemisches ein Dispergiermittel, z.B. Methyl-Zellulose enthält.8. The method according to claim 7, characterized in that the solution and / or slurry of the salt mixture is a dispersant, e.g. Contains methyl cellulose. 9. Verfahren nach einem der obigen Ansprüche, dadurch gekennzeichnet, daß der Lösung und/oder Aufschlämmung des Salzgemisches ein die Benetzung der Innenwand der keramischen Form verbesserndes Hilfsmittel, z.B. ein Tensid zugegeben wird.9. The method according to any one of the above claims, characterized in that the solution and / or slurry of the salt mixture is an auxiliary agent which improves the wetting of the inner wall of the ceramic mold, e.g. a surfactant is added.
EP86104247A 1985-04-03 1986-03-27 Method of casting aluminium alloys Expired - Lifetime EP0198290B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3512118 1985-04-03
DE19853512118 DE3512118A1 (en) 1985-04-03 1985-04-03 METHOD FOR GENERATING AN IMPROVED FINE-NARROWNESS OF THE PRIMARY FABRIC AND / OR THE EUTEKTIKUM OF CASTING PARTS

Publications (3)

Publication Number Publication Date
EP0198290A2 true EP0198290A2 (en) 1986-10-22
EP0198290A3 EP0198290A3 (en) 1987-06-24
EP0198290B1 EP0198290B1 (en) 1990-05-30

Family

ID=6267164

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86104247A Expired - Lifetime EP0198290B1 (en) 1985-04-03 1986-03-27 Method of casting aluminium alloys

Country Status (9)

Country Link
EP (1) EP0198290B1 (en)
JP (1) JPS61293653A (en)
BR (1) BR8601478A (en)
CA (1) CA1288210C (en)
DE (2) DE3512118A1 (en)
ES (1) ES8703097A1 (en)
IL (1) IL78279A0 (en)
SU (1) SU1760973A3 (en)
ZA (1) ZA862393B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0277577A2 (en) * 1987-02-05 1988-08-10 Thyssen Guss Ag Investment casting mould for aluminium or its alloys
DE3821204A1 (en) * 1988-06-23 1989-12-28 Winkelstroeter Dentaurum Inoculant mixture for coating casting moulds for the production of dental cast skeletons
GB2316640A (en) * 1996-08-30 1998-03-04 Triplex Lloyd Plc Fine grained castings using nucleating agent on mould surface
EP2158986A1 (en) * 2008-08-29 2010-03-03 Peugeot Citroën Automobiles Société Anonyme Lost-wax pattern casting process and lost-wax pattern for this process
WO2017106302A1 (en) * 2015-12-18 2017-06-22 Ask Chemicals L.P. Molding materials for non-ferrous casting

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4308614A1 (en) * 1993-03-18 1994-09-22 Fritz Winter Eisengieserei Ohg Method for producing workpieces made of cast iron, and hollow castings produced accordingly

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE963642C (en) * 1944-09-30 1957-05-09 Siemens Ag Process for influencing the surface of cast bodies
US3157926A (en) * 1964-02-14 1964-11-24 Howe Sound Co Making fine grained castings
US3259948A (en) * 1962-04-09 1966-07-12 Howe Sound Co Making fine grained castings
DE1433969B2 (en) * 1963-11-19 1973-02-08 Larsson, Rune, Sandviken (Schweden) FLUORINE PROTECTIVE LAYER FOR CASTING FORMS AND THE PROCESS FOR THEIR PRODUCTION

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1265356B (en) * 1965-02-26 1968-04-04 Henry H Harris Mold
NL126286C (en) * 1965-07-29

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE963642C (en) * 1944-09-30 1957-05-09 Siemens Ag Process for influencing the surface of cast bodies
US3259948A (en) * 1962-04-09 1966-07-12 Howe Sound Co Making fine grained castings
DE1433969B2 (en) * 1963-11-19 1973-02-08 Larsson, Rune, Sandviken (Schweden) FLUORINE PROTECTIVE LAYER FOR CASTING FORMS AND THE PROCESS FOR THEIR PRODUCTION
US3157926A (en) * 1964-02-14 1964-11-24 Howe Sound Co Making fine grained castings

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0277577A2 (en) * 1987-02-05 1988-08-10 Thyssen Guss Ag Investment casting mould for aluminium or its alloys
EP0277577A3 (en) * 1987-02-05 1988-11-30 Thyssen Guss Ag Investment casting mould for aluminium or its alloys
DE3821204A1 (en) * 1988-06-23 1989-12-28 Winkelstroeter Dentaurum Inoculant mixture for coating casting moulds for the production of dental cast skeletons
GB2316640A (en) * 1996-08-30 1998-03-04 Triplex Lloyd Plc Fine grained castings using nucleating agent on mould surface
US5983983A (en) * 1996-08-30 1999-11-16 Triplex Llyod Limited Method of making fine grained castings
EP2158986A1 (en) * 2008-08-29 2010-03-03 Peugeot Citroën Automobiles Société Anonyme Lost-wax pattern casting process and lost-wax pattern for this process
FR2935275A1 (en) * 2008-08-29 2010-03-05 Peugeot Citroen Automobiles Sa LOST MODEL MOLDING PROCESS, LOST MODEL FOR THIS PROCESS
WO2017106302A1 (en) * 2015-12-18 2017-06-22 Ask Chemicals L.P. Molding materials for non-ferrous casting
US9889497B2 (en) 2015-12-18 2018-02-13 Ask Chemicals L.P. Molding materials for non-ferrous casting
CN108778557A (en) * 2015-12-18 2018-11-09 亚世科化学有限责任公司 Modeling Material for non-ferrous metal foundries
KR20180125447A (en) * 2015-12-18 2018-11-23 에이에스케이 케미칼스 엘엘씨 Molding materials for non-ferrous casting
KR102545134B1 (en) 2015-12-18 2023-06-19 에이에스케이 케미칼스 엘엘씨 Molding materials for non-ferrous castings

Also Published As

Publication number Publication date
SU1760973A3 (en) 1992-09-07
JPS61293653A (en) 1986-12-24
BR8601478A (en) 1986-12-09
ES553681A0 (en) 1987-02-16
CA1288210C (en) 1991-09-03
IL78279A0 (en) 1986-07-31
DE3512118A1 (en) 1986-10-16
DE3671607D1 (en) 1990-07-05
ES8703097A1 (en) 1987-02-16
EP0198290B1 (en) 1990-05-30
EP0198290A3 (en) 1987-06-24
ZA862393B (en) 1986-11-26

Similar Documents

Publication Publication Date Title
DE2228841C3 (en) Method and device for rapid cooling and solidification of a melt of refractory oxide material
EP2248614B1 (en) Dispersion, slip and method for producing a casting mould for precision casting using the slip
EP2841220A1 (en) Method for producing moulds and cores for metal casting and moulds and cores produced according to this method
EP1973681A1 (en) Water-based liquid size containing a seeding agent
DE3824849A1 (en) PRESSURIZED POLYCRYSTALLINE MIXING MATERIALS BASED ON HEXAGONAL BORNITRIDE, OXIDES AND CARBIDES
DE4110145C2 (en)
DE3009490C2 (en)
DE2630541A1 (en) PROCESS FOR MANUFACTURING AN ALUMINUM CASTING PART WITH WEAR-RESISTANT SURFACE PARTS
EP0198290B1 (en) Method of casting aluminium alloys
DE3130920A1 (en) &#34;ELIGIBLE COPPER ALLOYS&#34;
DE102016211948A1 (en) Core-shell particles for use as filler for feeder masses
US4766948A (en) Process for casting aluminum alloys
WO1995005490A1 (en) Molten mass treating agent, its production and use
DE2854958A1 (en) Composite cast cylinder blocks for IC engine - consists of aluminium alloy block cast round liners made of wear resistant, hypereutectic aluminium silicon alloy
DE3200104C2 (en) Casting device for the production of alloyed metal castings
DE10392662B4 (en) Copper-nickel-silicon two-phase quenching substrate
EP0629458B1 (en) Embedding material for casting
DE1198496B (en) Process for the production of castings with a fine-grained crystal structure
EP0277577B1 (en) Investment casting mould for aluminium or its alloys
DE19908952A1 (en) Ceramic moulding material for production of vessels and moulds for melting and casting of e.g. superalloys, titanium and titanium alloys
DE10011977C1 (en) Sizing agent for coating sand castings for the production of castings from magnesium and magnesium alloys
DE2652434A1 (en) KAEFIGLAEUFER OR -LADDER FOR A SHORT-CIRCUIT ANCHORED INDUCTION MOTOR AND PROCESS FOR ITS MANUFACTURING
DE112004001542B4 (en) Copper-nickel-silicon two-phase quench substrate
DE19800433A1 (en) Aluminum plain bearing alloy
DE4107919C1 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19860416

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19890630

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 3671607

Country of ref document: DE

Date of ref document: 19900705

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19910218

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19910220

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910227

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910228

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910331

Year of fee payment: 6

26N No opposition filed
EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19920328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920331

Ref country code: CH

Effective date: 19920331

Ref country code: BE

Effective date: 19920331

BERE Be: lapsed

Owner name: THYSSEN INDUSTRIE A.G.

Effective date: 19920331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19921001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930215

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930219

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940327

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940525

Year of fee payment: 9

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19941130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 86104247.1

Effective date: 19921005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19951201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050327