WO2009007093A2 - Système d'enduit de protection pour outils de coulée - Google Patents

Système d'enduit de protection pour outils de coulée Download PDF

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Publication number
WO2009007093A2
WO2009007093A2 PCT/EP2008/005560 EP2008005560W WO2009007093A2 WO 2009007093 A2 WO2009007093 A2 WO 2009007093A2 EP 2008005560 W EP2008005560 W EP 2008005560W WO 2009007093 A2 WO2009007093 A2 WO 2009007093A2
Authority
WO
WIPO (PCT)
Prior art keywords
casting
sizing composition
composition according
size
mold
Prior art date
Application number
PCT/EP2008/005560
Other languages
German (de)
English (en)
Other versions
WO2009007093A3 (fr
Inventor
Manfred Laudenklos
Original Assignee
Ks Aluminium-Technologie Gmbh
Gelita 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 Ks Aluminium-Technologie Gmbh, Gelita Ag filed Critical Ks Aluminium-Technologie Gmbh
Publication of WO2009007093A2 publication Critical patent/WO2009007093A2/fr
Publication of WO2009007093A3 publication Critical patent/WO2009007093A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns

Definitions

  • the present invention relates to a sizing composition, the use thereof for protecting casting tool contours and casting tool contours provided with said sizing composition.
  • Casting transforms molten bath materials into geometrically determined objects with specific workpiece properties.
  • Most products of the iron and steel industry as well as the materials of the non-ferrous metal industry go through casting processes for the first shaping.
  • a prerequisite for the production of castings is, among other things, the production of partly very complicated casting molds for receiving the melt.
  • the molds are subdivided into lost molds, which are usually made of a mineral, refractory, granular base material with a binder and often several other additives, e.g. To obtain good casting surfaces, exist and destroyed after each casting, and permanent molds, with each of which a large number of castings can be produced.
  • cast iron, unalloyed and alloyed steels, as well as copper, aluminum, graphite, sintered metals and ceramic materials have proven successful as mold material for permanent molds.
  • a method for producing casting molds comprises, for example, the production of a base or core, for example of foundry sand and the application of a refractory inorganic constituents containing coating (mold coating), which is also called “sizing", at least on those surfaces of the basic shape and / or Core materials that come into contact with the cast metal
  • the coating compositions have, inter alia, the purpose of To influence molding surface, so to improve the casting appearance, to influence the casting metallurgically and / or to avoid casting defects.
  • the sizing composition serves in a first line in particular to support the metal flow, which in turn leads to a uniform filling of the permanent mold.
  • these coatings or sizing functions to chemically isolate the mold from the liquid metal during casting, thereby preventing any adhesion and allowing or facilitating the subsequent separation of mold and casting.
  • the sizing protects against corrosion that common metallic materials show against aluminum and other non-ferrous metals at typical processing temperatures.
  • the sizing composition also serves to avoid residues on the permanent mold, which can lead to inaccuracies in the form.
  • a metal mold is subjected to such thermal stresses in the course of successive casting operations that it is prematurely destroyed.
  • the heat transfer through the sizing can be used selectively to influence the cooling of the casting.
  • metal parts such as cast iron
  • the large-scale casting and the centrifugal casting process are used. In the case of the large casting process, enormous metallostatic pressures prevail on the mold and core, which are exposed to the temperature load for a very long time.
  • the sizing takes on a very exposed protective function in order to avoid penetration of the metal into the molding sand (penetration), cracking of the cores (leaf ribs) or reaction with the molding sand (distortions).
  • penetration penetration of the metal into the molding sand
  • cores cores
  • disortions reaction with the molding sand
  • centrifugal casting the casting metal is filled into a rotating around its axis, tubular or annular mold in which it is formed under the action of centrifugal force, for example, to cans, rings and pipes. It is imperative that the casting be fully solidified before demolding so that a fairly long contact time between mold and casting is required.
  • the mold is coated with an insulating size in the form of a single-layer or multi-layer coating.
  • the commonly used sizings contain as basic materials such as clays, quartz, kieselguhr, cristobalite, tridymite, aluminum silicate, zirconium silicate, mica, chamotte and also coke and graphite. These bases are the purportive portion of the sizings which cover the mold surface and close the pores against the penetration of the cast metal.
  • a long known and used in sizing compositions material is boron nitride (BN), which is similar in structure to its crystal structure as graphite. Like graphite, it has a low wettability compared to many substances, such as silicate melts or molten metals.
  • DE 101 24 434 A1 discloses a wear protection layer in which functional materials are incorporated in a binder matrix.
  • This so-called functional coating consists of an inorganic matrix phase, which consists at least largely of a phosphate, and a functional material embedded therein, for example, a metal, graphite, a hard material, a dry lubricant, an aluminum oxide, a silicon carbide, ect. can be.
  • a liquid component which may be, for example, water, a functional material in powder form and is added to produce a phosphate with phosphoric acid.
  • Such a composite matrix solution with the liquid component and the phosphate may also be referred to as gel due to their consistency.
  • the material After coating a material with this matrix solution, the material undergoes a heat treatment, so that a firmly adhering functional coating is formed on the base material.
  • DE 10 2005 042 475 A1 relates to a metallic, iron-containing permanent mold, in particular a permanent mold made of steel, which can be acted upon by a liquid or flowable aluminum material, wherein on at least one surface of the permanent mold a layer consisting of
  • a disadvantage of this Schlichtezusammenstzung known from the prior art is that they only a limited extend the life of the casting tool contours used, hereinafter also referred to as permanent molds.
  • the casting quality of the resulting castings is often unsatisfactory and in need of improvement.
  • the accuracy of the mass of the castings is often unsatisfactory in the size compositions described above.
  • the amount of required size is relatively high, so that usually the material consumption is relatively high.
  • excessive formation of gas due to decomposition of the size must not occur, which would lead to a porosity of the molded parts.
  • the sizing composition should ultimately also contain no hazardous or toxic substances.
  • the size composition according to the invention should prolong the life of the permanent molds used.
  • the cast quality of the resulting castings should preferably be improved by the size composition according to the invention.
  • the accuracy of the mass of the castings is to be improved by using a corresponding sizing composition.
  • the solution to these objects is based on a sizing composition which is characterized in that it comprises ceramic materials and at least one binder selected from the group consisting of waterglass-based binders and refractory binders in combination with fluoride-containing constituents.
  • the size composition of the invention By using the size composition of the invention on a permanent mold, the above objects are achieved.
  • the use of the composition of the invention in the permanent form the Long-term stability of the permanent form increased.
  • the size composition of the invention generally improves the casting quality of the resulting castings and the accuracy of the mass of the castings.
  • the size composition according to the invention contains at least one ceramic material.
  • This ceramic material is generally selected from the group consisting of diatomite, kaolins, calcined kaolins, kaolinite, metakaolinite, pyrophyllite, mica, zirconium oxides, zirconium silicate (zircon flour, zirconium), alumina, andalusite, chamotte, iron oxides, kyanite, bauxite , Olivine, quartzes, talc, graphites, boron nitride, silicas, titanium oxides, zinc oxides and carbon blacks, as well as clays and minerals containing them.
  • the particle size of the ceramic materials used in the size composition according to the invention can vary within wide limits. However, the size is generally preferably 2 to 15 ⁇ m.
  • the size composition according to the invention also comprises at least one binder selected from the group consisting of binders based on water glass and refractory binders in combination with fluoride-containing constituents and mixtures thereof.
  • a binder in a suitable sizing composition is to allow binding of the ingredients of the sizing composition after drying the sizing applied to a casting mold.
  • the binder cures irreversibly and thus provides an abrasion resistant coating on the mold.
  • the abrasion resistance is of great importance for the finished coating, since the coating can be damaged in the absence of abrasion resistance.
  • the binder should not be softened by atmospheric moisture.
  • curing of the binder is carried out in a manner known per se.
  • a water glass can be used as the binder.
  • a mixture of high-purity quartz sand and potassium carbonate or sodium carbonate is melted with CO 2 evolution.
  • the melting temperature is 1350 to 1480 0 C depending on the ratio of sand to alkali carbonate.
  • the cooled glass is ground to a powder (solid water glass).
  • liquid water glass can also be used as a clear, alkaline solution or as a gelatinous to solid mass for use. Liquid water glass is obtained by dissolving the solid water glass in water at high temperatures (150 "C).
  • Refractory binder systems can also be used.
  • Refractory binders are usually present as a powder, which are ground up to particle sizes up to about 80 to 125 microns, depending on the application.
  • the choice of refractory binder or binders is determined primarily by the material to be cast. Here, not only the casting temperatures must be considered, but also possible reactions between the refractory binders and the respective casting metals and the molding materials.
  • the refractory filler should preferably be substantially inert and should not form low melting compounds. He should also have a low thermal expansion.
  • Suitable refractory binders in the context of the present invention are, for example, graphite, coke, quartz, alumina, magnesite, mica, talc, pyrophyllite, zirconium, olivine, mullite and phosphate-containing refractory binders.
  • phosphate-containing refractory binders are preferred.
  • phosphate-containing refractory binders are used in the sizing composition of the present invention, they are preferably selected from the group consisting of monoaluminum phosphate, monozinc phosphate, monomagnesium phosphate, sodium phosphate, boron phosphate, and any mixtures thereof.
  • fluoride-containing components in combination with the above binders in the sizing compositions according to the invention still fluoride-containing components can be used.
  • suitable fluoride-containing constituents are zirconium fluoride or H 2 ZrF 6 .
  • Further possible fluoride-containing constituents are H 2 TiF 6 , H 2 HfF 6 , H 2 SiF 6 , H 2 GeF 6 , H 2 SnF 6 and HBF 4 .
  • Optionally commonly used dispersants may be added to the sizing composition.
  • the dispersants are preferably in an amount of 0.01 to 10 wt .-%, particularly preferably 0.1 to 7.5 wt .-%, in particular 0.5 to 5 wt .-%, each based on the size composition of the invention, used.
  • examples of dispersants which can be used are hexasodium tetrapolyphosphate or sodium polyacrylate.
  • the sizing composition is added to a gelatin-based dispersant.
  • a stabilization can be achieved and the reaction rate is improved.
  • the gelatin preferably has the task of providing a potential balance in dispersing and accelerating the reaction. To explain the potential equalization of the gelatin in the binder phase, reference is made to the Richardson-Ellingham diagram known to those skilled in the art, from which the potential differences of the individual chemical compounds used can be read.
  • serve magnesium and calcium in which it is the main components of the gelatin according to the invention used in the examples Gelita ® is (3950 mg calcium / kg of gelatin and 1500 mg magnesium / kg gelatin) for stabilizing the structural parts and primary parts in partial dissolution of the hot base material by the Sighting, so that a control of the bonding of the coating to the base material is possible.
  • a gelatin-based additive is essentially understood as meaning a material which contains gelatin.
  • Gelatin is a polypeptide obtained primarily by hydrolysis of collagen under acidic (gelatin type A) or alkaline (gelatin type B) conditions.
  • Gelatine is a taste-neutral animal protein (polypeptide) that contains all essential amino acids in addition to tryptophan.
  • polypeptide a taste-neutral animal protein
  • the initially insoluble connective tissue of (especially) skin and bone of pigs and cattle but also of poultry and fish is subjected to a digestion process (hydrolysis), which splits the peptide bonds, so that the thus rendered water-soluble kaollagen can be extracted.
  • the digestion can be carried out by boiling or by treatment with acids and bases and subsequent extraction (industrial production).
  • Gelatin usually contains 1 to 2 wt .-% minerals and up to 15 wt .-% water.
  • the gelatin-containing material on the basis of which the sizing composition is preferably prepared, is preferably predominantly gelatin. forms. These generally include gelatin contents of 60% by weight or more, preferably 75% by weight or more, in particular 90% by weight or more.
  • the material may contain, for example, further biopolymers such as alginates or hyaluronic acid in order to adapt the property profile even more specifically to a specific application.
  • the gelatin-containing material additionally comprises a plasticizer.
  • a plasticizer e.g. Glycerol, oligoglycerols, oligoglycols and sorbitol, with glycerol being most preferred.
  • the dispersing material is formed substantially completely from gelatin.
  • gelatin which is sold under the brand name Gelita ®.
  • the sizing compositions of the invention may further optionally comprise one or more further components, e.g. Wetting agents, defoamers, pigments, dyes, biocides, dispersants and lubricants.
  • further components e.g. Wetting agents, defoamers, pigments, dyes, biocides, dispersants and lubricants.
  • Wetting agents which may be used are preferably anionic and non-anionic surfactants of medium and high polarity (HSB value of 7 and higher) known to the person skilled in the art.
  • An example of a wetting agent that can be used in the present invention is disodium dioctylsulfosuccinate.
  • the wetting agents are generally used in an amount of 0.01 to 1 wt .-%, preferably 0.05 to 0.3 wt .-%, each based on the size composition according to the invention.
  • Defoamers or antifoam agents are used to prevent foaming during the preparation of the coating composition and during its application. Foaming on application of the sizing composition can result in uneven layer thickness and holes in the coating.
  • defoamers for example, silicone or mineral oil can be used.
  • defoamers are present in an amount of generally from 0.01 to 1% by weight, based on preferably 0.05 to 0.3 wt .-%, each based on the size composition of the invention used.
  • any commonly used pigments and dyes may be used. These are optionally added in order to achieve a different contrast, for example between different layers, or to bring about a greater separation effect of the size of the casting.
  • pigments are red and yellow iron oxide and graphite.
  • dyes are commercially available dyes such as the Luconyl ® color series from BASF.
  • the dyes and pigments are usually used in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the size composition according to the invention.
  • Sizing compositions whose carrier liquid consists mainly of water, so-called water sizing, are usually added biocides in order to prevent bacterial attack and thus to avoid a negative impact on the rheology and the binding force of the binding agents.
  • biocides to be used are formaldehyde, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isotbiazolin-3-one (CIT) and 1,2-benzisothiazoline-3 on (BIT).
  • MIT, BIT or a mixture thereof are used.
  • the biocides are usually used in an amount of 0.01 to 0.5 wt.%, Preferably 10 to 1000 ppm, in particular from 50 to 500 ppm, each based on the size composition of the invention.
  • the sizing compositions of the invention may contain one or more nonionic and / or ionic lubricants as part of component IV), such as polyalkylene glycol ethers of fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids having 12 to 18 carbon atoms, polyalkylene glycols, higher fatty acid amides 12 to 18 Carbon atoms of polyalkylene glycols and / or alkylene lenaminen, quaternary nitrogen compounds, eg ethoxylated imidazolinium salts, mineral oils and waxes.
  • nonionic and / or ionic lubricants as part of component IV), such as polyalkylene glycol ethers of fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids having 12 to 18 carbon atoms, polyalkylene glycols, higher fatty acid amides 12 to 18 Carbon
  • lubricants may also be selected from the group consisting of boron nitride, magnesium aluminum silicates and molybdenum disulphide.
  • the lubricants are preferably used in a total concentration of from 0.05 to 1.5% by weight, based on the total size composition.
  • the particle size is preferably 2 to 15 ⁇ m.
  • Another object of the present invention is the use of the sizing composition according to the invention as a release agent for producing a layer on a permanent mold.
  • the present invention relates to a permanent mold in which at least part of the surface of the permanent mold has a sizing composition according to the invention.
  • the sizing composition can be applied in a continuous layer on the permanent mold.
  • the sizing composition is applied in a non-continuous layer on the permanent mold.
  • a continuous application of the size composition according to the invention in the context of the present invention is understood to mean that the size composition is applied contiguously to the permanent form, while the term non-continuous application is used when the individual size final sizing fractions are interrupted by an area which is not provided with a finishing order.
  • the size according to the invention can be applied only in the region of the permanent mold, which is later also in contact with the casting material.
  • complete coverage of the permanent form by the sizing is also possible.
  • the thickness of the size composition on the permanent mold is not particularly limited and may take different values depending on the application of the size compositions of the present invention. Suitable layer thicknesses are, for example, 1 to 80 ⁇ m, more preferably 25 to 60 ⁇ m.
  • cast iron, unalloyed and alloyed steels, as well as copper, aluminum, graphite, sintered metals and ceramic materials have proven successful as mold material for permanent molds.
  • the permanent mold according to the invention is preferably metal-containing.
  • the permanent mold according to the invention contains iron.
  • the permanent mold according to the invention is designed so that it can be used in a die-casting, low-pressure casting, gravity casting and / or squeeze casting process.
  • a die-casting process is understood to mean a process in which the liquid melt is pressed under high pressure of approximately 10 to 200 MPa and at a very high speed of up to 120 m / s into a die casting mold (casting mold) then cooled.
  • a low-pressure casting process is understood to mean a casting process in which a molten metal is conveyed via a riser pipe into a mold (mold) which is placed above the melt container.
  • the conveyance of the melt takes place by increasing the pressure in the sealed furnace chamber.
  • the melt rises in the riser and the mold is filled.
  • the pressure is lowered again and the melt located in the riser falls back into the crucible.
  • the working pressure is generally a maximum of one bar overpressure.
  • a squeeze casting is understood to mean a pressure casting process which is based on a slower continuous mold filling and high metal pressures.
  • the advantage consists in the laminar mold filling and the associated pores and voids freedom of the component that is complemented by the squeezing (repressing during solidification).
  • the present invention relates to a process for the preparation of a size on a permanent mold, characterized in that applying the above-described sizing composition to a permanent mold.
  • the cold permanent form can be applied to the size composition according to the invention by spraying on the size composition and heating the permanent mold.
  • This wear layer generally comprises a structural element which can act as a binder at the same time.
  • the structural element may be, for example, amorphous silicic acids.
  • this wear layer may comprise primary particles selected from the group consisting of boron nitride, mica, magnesium aluminum silicate, ammonium hydrogen carbonate, titanium dioxide, bismuth, and any mixtures thereof.
  • the wear layer may further comprise a dispersing agent, for example selected from the group consisting of proteins, inorganic fines and metal ions (gelatin).
  • the wear layer can be formed as described in DE 101 24 434 A1.
  • Corresponding wear layers comprise, for example as functional material, a metal, a polymer, graphite, a hard material such as a metal nitride, a metal oxide, a metal carbide, a metal carbonitride, a dry lubricant or a ceramic, in particular Si, ZrO 2 , Al 2 O 3 , SiO 2 , TiO 2 , TiN, Teflon, polytetrafluoroethylene, polyethylene, polyamide, boron nitride, silicon nitride, MoS 2 , MoSi 2 or chromium oxide.
  • a further subject of the present invention are furthermore combinations of the size according to the invention, which are obtained starting from the size composition according to the invention, with the wearing layer described in more detail above.

Abstract

L'invention concerne une composition d'enduit qui comprend des matériaux céramiques et au moins un liant sélectionné dans l'ensemble constitué des liants à base de verre liquide et des liants réfractaires combinés avec des composés contenant des fluorures.
PCT/EP2008/005560 2007-07-11 2008-07-08 Système d'enduit de protection pour outils de coulée WO2009007093A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007032632.9 2007-07-11
DE102007032632 2007-07-11

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WO2009007093A2 true WO2009007093A2 (fr) 2009-01-15
WO2009007093A3 WO2009007093A3 (fr) 2009-03-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016211930A1 (de) * 2016-06-30 2018-01-04 Wobben Properties Gmbh Schlichtezusammensetzung zur Herstellung von Formüberzügen auf verlorenen Formen bzw. auf Kernen für den Eisen- und Stahlguss
CN111570719A (zh) * 2020-05-20 2020-08-25 无锡卡仕精密科技有限公司 一种用于精密铸造的硅溶胶改性涂料
WO2021209424A1 (fr) 2020-04-15 2021-10-21 Peak Deutschland Gmbh Utilisation d'un solvant pour la production de colles, procédé de production d'une colle, colle et utilisation de celle-ci
DE102009009559B4 (de) 2009-02-19 2022-02-17 Ceranovis Gmbh Verfahren zum Verlängern der Standzeit von technischen Oberflächen
DE202023103207U1 (de) 2023-06-12 2023-06-20 Peak Deutschland Gmbh Schlichte und deren Verwendung

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WO2007062703A1 (fr) * 2005-09-07 2007-06-07 Ks Aluminium-Technologie Ag Couche de protection pour surface en ceramique d'un outil de coulee

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009009559B4 (de) 2009-02-19 2022-02-17 Ceranovis Gmbh Verfahren zum Verlängern der Standzeit von technischen Oberflächen
DE102016211930A1 (de) * 2016-06-30 2018-01-04 Wobben Properties Gmbh Schlichtezusammensetzung zur Herstellung von Formüberzügen auf verlorenen Formen bzw. auf Kernen für den Eisen- und Stahlguss
WO2018002206A1 (fr) 2016-06-30 2018-01-04 Wobben Properties Gmbh Composition d'enduit noir destiné à la fabrication de revêtements de moules perdus ou de noyaux destinés au moulage de fonte et au moulage d'acier
US11027328B2 (en) 2016-06-30 2021-06-08 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Refractory coating composition for making facings on temporary molds or on cores for iron and steel casting operations
WO2021209424A1 (fr) 2020-04-15 2021-10-21 Peak Deutschland Gmbh Utilisation d'un solvant pour la production de colles, procédé de production d'une colle, colle et utilisation de celle-ci
DE102020110290A8 (de) 2020-04-15 2021-12-30 Peak Deutschland Gmbh Verwendung eines Lösemittels zur Herstellung von Schlichten, ein Verfahren zur Herstellung einer Schlichte, eine Schlichte und deren Verwendung
CN111570719A (zh) * 2020-05-20 2020-08-25 无锡卡仕精密科技有限公司 一种用于精密铸造的硅溶胶改性涂料
DE202023103207U1 (de) 2023-06-12 2023-06-20 Peak Deutschland Gmbh Schlichte und deren Verwendung

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