EP1993755B1 - Couche de demoulage pour couler des metaux non ferreux - Google Patents

Couche de demoulage pour couler des metaux non ferreux Download PDF

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Publication number
EP1993755B1
EP1993755B1 EP07722819.5A EP07722819A EP1993755B1 EP 1993755 B1 EP1993755 B1 EP 1993755B1 EP 07722819 A EP07722819 A EP 07722819A EP 1993755 B1 EP1993755 B1 EP 1993755B1
Authority
EP
European Patent Office
Prior art keywords
release agent
mold release
mold
layer
permanent
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.)
Not-in-force
Application number
EP07722819.5A
Other languages
German (de)
English (en)
Other versions
EP1993755A1 (fr
Inventor
Manfred Laudenklos
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.)
Gelita AG
KS Huayu Alutech GmbH
Original Assignee
Gelita AG
KS Aluminium Technologie GmbH
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 Gelita AG, KS Aluminium Technologie GmbH filed Critical Gelita AG
Publication of EP1993755A1 publication Critical patent/EP1993755A1/fr
Application granted granted Critical
Publication of EP1993755B1 publication Critical patent/EP1993755B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/22—Dies; Die plates; Die supports; Cooling equipment for dies; Accessories for loosening and ejecting castings from dies
    • B22D17/2209—Selection of die materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/77—Controlling or regulating of the coating process

Definitions

  • the invention relates to a metallic, iron-containing permanent mold with a coating which can be acted upon by a liquid or a flowable aluminum material. Moreover, the invention relates to a release agent for producing such a layer, and to a method for producing such a layer on a surface of a permanent mold.
  • release agents for trouble-free operation.
  • various requirements set forth below are imposed on the release agents used in the process.
  • the release agent must serve to assist the metal flow, resulting in a uniform filling of the permanent mold and at the same time the release agent is used to improve the final formability of the cast parts.
  • the release agent serves to avoid residues on the permanent mold, which can lead to inaccuracies in the form.
  • the release agent During the pouring of the material into the permanent mold, no excessive gas formation may occur during the decomposition of the release agent, which would lead to a porosity of the molded parts.
  • the release agent must ultimately contain no dangerous or toxic substances. Depending on the fulfillment of these requirements, the quality of the release agent is measured.
  • boron nitride A long known and used in release agents 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. Therefore, there are many studies on non-adherent layers based on boron nitride in order to use them for casting processes. The problem with this use, however, is that it is not possible to permanently apply boron nitride to forms, in particular of a complex nature.
  • a method for permanent application of a temperature-stable, corrosion-resistant mold release layer is in DE 198 42 660 A1 described. Here, a boron nitrite powder is applied by means of electrostatic coating on the surface of a permanent mold.
  • a wear protection layer is known, are integrated in the functional materials 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, a Alumina, a silicon carbide, etc. may 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.
  • the object of the present invention is to develop a long-term stable layer on a metallic, iron-containing permanent form, which enters into a chemical bond with the base material of Treasureform and thus meets the requirements for a release agent or even goes beyond these requirements, by casting errors by the Formation of oxide skins during the casting process can be avoided. Moreover, it is an object of the invention to provide a release agent for producing such a layer, which is inexpensive to produce and easy to apply without the expense of equipment. Another object of the invention is to provide a method capable of producing such a layer and by means of Damage to the layer are easily healed.
  • the requirements for a release agent in the form of a long-term stable layer are particularly well met.
  • the metal flow is supported to the effect that the oxide skin of the aluminum material is broken up by the structural parts protruding from the layer and the liquid aluminum material can easily be distributed in the permanent form below the oxide layer.
  • the layer thus offers optimum conditions for filling the permanent mold.
  • the sliding parts of the form boron nitride (BN) serve as a sliding surface for the liquid or flowable aluminum and thus support the metal flow, they also serve at the same time to improve the Endform Marie of the cast components.
  • a firmly adhering layer is formed, wherein the solid composite is produced by the chemical bonding of the fluorides with the iron of the permanent material of the permanent mold.
  • This type of firm bonding of the layer with the base material of the permanent form prevents residues from adhering to the permanent mold, which could lead to dimensional inaccuracies.
  • Another advantage of the layer according to the invention is that the layer is excited at elevated temperatures to an increased polymerization. As a result, longer polymers form, on the one hand increase the adhesion and cohesion and on the other hand increase the elasticity of the layer.
  • the long-term stable and firmly adhering layer is therefore extremely elastic at higher temperatures, as occur during filling of the permanent mold, and can follow the changes in shape of the permanent mold elastically and thus advantageously without damage to the layer.
  • the release agent according to the invention offers the advantage that it can be produced cost-effectively on the basis of demineralized water and, on the other hand, is easy to apply to the tool due to its viscosity. in the simplest case, the release agent can be sprayed on the permanent mold. In addition, the release agent meets the requirements for a release agent in that no toxic substances are included, which can be disposed of only at high cost.
  • the object according to the invention with regard to the method for producing a layer is achieved in that the surface is first subjected to the release agent according to one of claims 6 to 13, and that subsequently the permanent mold is heated to a temperature of at least 200 ° C.
  • the fluoride chemically bonds with the iron of the base material and the zirconium fluoride forms polymers which form a firmly adhering layer on the surface of the permanent mold.
  • the advantage here is that the release agent, which consists of a completely desalinated water, at this temperature is already completely evaporated from the layer and thus there is no or very little gas formation when filling the permanent mold.
  • the polymerization is supported in increasing the temperature, so that as described above, another advantageous effect of the layer is generated.
  • the use of gelatin is particularly advantageous since this nanoparticles are formed independently.
  • the layer is very easy to heal, since defects in the layer are immediately lashed out after a renewed application of the permanent mold with the release agent.
  • new iron fluoride is formed and by the temperature of the permanent form zirconium fluoride polymerizes, so that the layer completely heals.
  • a layer is formed which has a thickness of about 1 to 80 .mu.m, layer thicknesses between 30 and 50 .mu.m are preferred, but this in turn Deployment case is dependent.
  • the layer thickness is dependent on the application, that is, on the casting process, wherein the thinnest layers are used for die casting and the thickest layers for low pressure. During die casting, the thinnest layers are applied, since here a good heat transfer to the permanent mold is deliberately set, in order to allow rapid solidification of the casting. In the combined so-called squeeze-casting process, an average thickness is set, since in this case the casting mold is slowly filled and then subjected to a high pressure.
  • the existing on the surface of the permanent mold layer is chemically connected by means of the iron fluoride with the base material.
  • the iron fluoride thus acts as an adhesive between the layer and the base material.
  • the structural parts of the form Al 2 O 3 and / or SiO 2 and / or TiO 2 and / or ZrO 2 have a size of about 80 nm until 200nm and hook against each other and form a layer on the base material.
  • the term structural parts is selected specifically, since particles are preferably used which are not smooth but have a structured surface.
  • the primary parts of the form Al 2 O 3 and / or SiO 2 and / or zinc oxide and / or titanium dioxide and / or zirconium dioxide and / or cerium oxide, which are present in a size of 1 nm to 10 nm, preferably and very easy.
  • the much larger sliding parts of the boron nitrite lie between the structural parts in the layer and are held by the composite of structural parts with polymers. Because of its fractile structure, the layer thus constructed has a self-interlocking effect, but the essential bond between the iron fluoride and the structural parts, the primary parts and the sliding parts is created by the polymerized zirconium fluoride.
  • the chains of the polymers provide the cohesion between the chemically bound iron fluoride, the structural parts, the primary parts and the sliding parts.
  • the polymers used according to the invention polymerize at about 200 ° C. and have a glazing temperature of about 830 ° C.
  • the liquid aluminum has a temperature of about 730 ° C and thus does not reach the glazing temperature of the polymers. It is thus an extremely stable, created for the casting of aluminum materials very suitable system as a layer structure.
  • the iron fluorides serve as an adhesive to the base material of the permanent mold and the primary parts are advantageously used to close the gaps between the structural cells, thus producing a very smooth surface. An adhesion of the liquid casting material is thus almost almost impossible.
  • the Structural parts are available in a size of 80nm to 200nm and stand out as edges from the layer.
  • the structurally highly structured structural parts tear cracks in the oxide layer of the liquid aluminum and grind the oxide skin, so that the oxide skin is crushed into minute parts and thus not present as lattice defects in the structural structure of the casting.
  • An advantage of the structural parts used according to the invention is thus that the oxide skin is destroyed and comminuted.
  • the sliding parts which are in the form of boron nitride, are much larger in size than the primary and structural parts.
  • the structural parts form the structural parts with a weight percentage of up to 10% in the liquid release agent, the largest part of the layer.
  • the primary parts serve as fillers for the interstices and thus serve to smooth the layer.
  • the sliding parts present in a proportion by weight of up to 5%, are finely distributed in the structural parts and also occur on the surface of the layer. Due to the number of sliding parts, these do not form the largest surface of the layer but are very finely distributed, so that they serve as a lubricant for a casting but primarily for demolding the permanent mold and for removing the casting.
  • the removal from the mold is advantageously facilitated by the use of the layer according to the invention, since, on the one hand, a very smooth surface is present on the layer through the structural parts and the smoothing primary parts and, at the same time, a lubricant is provided by the sliding parts.
  • the zirconium fluoride polymerizes and a long-term stable layer is formed on the surface of the permanent mold.
  • a usual temperature for preheating during die casting is a temperature between 220 ° C and 280 ° C, so that here an optimum temperature for the polymerization of the release agent is present.
  • the preheating temperatures are still above 300 ° C, so that a layer is also formed here.
  • the liquid metal at a temperature of about 720 ° C to 730 ° C when casting aluminum is below the glass transition temperature. But the Thixocasting is above 200 ° C and thus the use of the layer according to the invention in this method is also conceivable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mold Materials And Core Materials (AREA)
  • Lubricants (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Moule permanent métallique ferreux, en particulier un moule permanent en acier, sur lequel peut être appliqué un matériau d'aluminium liquide ou coulant,
    caractérisé en ce que
    sur au moins une surface du moule permanent est présent une couche formée par
    - le fluorure de fer chimiquement lié avec un matériau de base dudit moule permanent,
    - des parties structurelles en forme d'un ou plusieurs des composés Al2O3, SiO2, TiO2 et ZrO2 en une fraction de 80 nm à 200 nm et
    - un polymère en fluorure de zirconium polymérisé entourant au moins partiellement lesdites parties structurelles.
  2. Moule permanent selon la revendication 1, caractérisé en ce que des parties de glissement en forme de nitrure de bore et/ou de silicate de magnésium et aluminium et/ou de disulfure de molybdène de 2 µm à 15 µm sont présentes dans ladite couche.
  3. Moule permanent selon l'une ou les deux revendication 1 et 2, caractérisé en ce que des parties primaires en forme de Al2O3, SiO2, ZnO, ZrO2, TiO2, CeO sont présentes dans ladite couche en une fraction de 2 nm à 80 nm, lesdites parties primaires étant incorporées dans les interstices entre les parties structurelles.
  4. Moule permanent selon l'une des revendications 1 à 3, caractérisé en ce que ladite couche existe sur la surface en une épaisseur de 1 µm à 80 µm, de préférence en une épaisseur de 25 µm à 60 µm.
  5. Moule permanent selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que ledit moule permanent est un moule permanent pour un procédé de moulage sous pression, moulage sous basse pression, moulage par gravité ou moulage par compression.
  6. Agent de démoulage pour la fabrication d'une couche sur un moule permanent, caractérisé en ce que
    ledit agent de démoulage est constitué par de l'eau déminéralisée et comprend les constituants suivants:
    - une ou plusieurs des compositions solutions de sodium, solution de potassium et chlorure d'aluminium,
    - un liant en fluorure de zirconium,
    - une proportion des parties structurelles en forme d'un ou plusieurs des composés Al2O3, SiO2, TiO2 et ZrO2 en une fraction de 80 nm à 200 nm et
    - un dispersant organique, de préférence la gélatine.
  7. Agent de démoulage pour la fabrication d'une couche sur un moule permanent selon la revendication 6, caractérisé en ce que ledit agent de démoulage contient une proportion des parties de glissement en forme de nitrure de bore et/ou de silicate de magnésium et aluminium et/ou de disulfure de molybdène en une fraction de 2 µm à 15 µm.
  8. Agent de démoulage selon l'une ou les deux revendications 6 et 7, caractérisé en ce que ledit agent de démoulage contient une proportion des parties primaires en forme de Al2O3, SiO2, ZnO, ZrO2, TiO2, CeO et/ou mica en une fraction de 2 nm à 80 nm.
  9. Agent de démoulage selon une ou plusieurs des revendications 6 à 8, caractérisé en ce qu'un pH de 4 à 5 est ajusté dans ledit agent de démoulage.
  10. Agent de démoulage selon une ou plusieurs des revendications 6 à 9, caractérisé en ce que la proportion du liant dans ledit agent de démoulage est inférieure ou égale à 5 % en poids.
  11. Agent de démoulage selon une ou plusieurs des revendications 6 à 10, caractérisé en ce que la proportion des parties structurelles dans ledit agent de démoulage est inférieure ou égale à 10 % en poids.
  12. Agent de démoulage selon une ou plusieurs des revendications 6 à 11, caractérisé en ce que la proportion des parties primaires dans ledit agent de démoulage est inférieure ou égale à 3 % en poids, de préférence entre 1 % en poids et 3 % en poids.
  13. Agent de démoulage selon l'une des revendications 6 à 12, caractérisé en ce que la proportion des parties de glissement dans ledit agent de démoulage est inférieure ou égale à 5 % en poids.
  14. Procédé de fabrication d'une couche sur une surface métallique ferreuse d'un moule permanent au moyen d'un agent de démoulage selon l'une quelconque des revendications précédentes,
    caractérisé en ce que
    d'abord, l'on applique ledit agent de démoulage sur ladite surface et qu'après, ledit moule permanent est chauffé à une température d'au moins 200°C de sorte qu'une liaison chimique entre ladite fluorure et le fer du matériau de base et une polymérisation du liant sont obtenues.
  15. Procédé selon la revendication 14, caractérisé en ce qu'un dommage dans la couche est recuit par une nouvelle application dudit agent de démoulage sur ledit moule permanent.
EP07722819.5A 2006-03-07 2007-02-15 Couche de demoulage pour couler des metaux non ferreux Not-in-force EP1993755B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006010876A DE102006010876A1 (de) 2006-03-07 2006-03-07 Formtrennschicht für das Gießen von Nichteisenmetallen
PCT/EP2007/001300 WO2007101528A1 (fr) 2006-03-07 2007-02-15 Couche de demoulage pour couler des metaux non ferreux

Publications (2)

Publication Number Publication Date
EP1993755A1 EP1993755A1 (fr) 2008-11-26
EP1993755B1 true EP1993755B1 (fr) 2013-07-17

Family

ID=38109514

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07722819.5A Not-in-force EP1993755B1 (fr) 2006-03-07 2007-02-15 Couche de demoulage pour couler des metaux non ferreux

Country Status (8)

Country Link
US (1) US8403024B2 (fr)
EP (1) EP1993755B1 (fr)
JP (1) JP4779025B2 (fr)
KR (1) KR20080111027A (fr)
CN (1) CN101500729B (fr)
BR (1) BRPI0708651A2 (fr)
DE (1) DE102006010876A1 (fr)
WO (1) WO2007101528A1 (fr)

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CN111360259A (zh) * 2020-03-10 2020-07-03 中信戴卡股份有限公司 一种异形泡沫铝填充铝合金空腔铸件的制备方法
CN116199510B (zh) * 2023-01-03 2024-03-15 三祥新材股份有限公司 一种电熔氧化锆生产过程中模具脱模方法
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Also Published As

Publication number Publication date
US8403024B2 (en) 2013-03-26
CN101500729B (zh) 2011-08-03
BRPI0708651A2 (pt) 2009-09-08
WO2007101528A1 (fr) 2007-09-13
JP2009528921A (ja) 2009-08-13
JP4779025B2 (ja) 2011-09-21
CN101500729A (zh) 2009-08-05
KR20080111027A (ko) 2008-12-22
EP1993755A1 (fr) 2008-11-26
US20090050288A1 (en) 2009-02-26
DE102006010876A1 (de) 2007-09-13

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