EP1993755B1 - Mold release layer for casting nonferrous metals - Google Patents

Mold release layer for casting nonferrous metals Download PDF

Info

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)
French (fr)
Other versions
EP1993755A1 (en
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/en
Application granted granted Critical
Publication of EP1993755B1 publication Critical patent/EP1993755B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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.

Landscapes

  • 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)

Description

Die Erfindung betrifft eine metallische, eisenhaltige Dauerform mit einer Beschichtung, die mit einem flüssigen oder einem fließfähigen Aluminiumwerkstoff beaufschlagbar ist. Darüber hinaus betrifft die Erfindung ein Trennmittel zur Herstellung einer derartigen Schicht, sowie ein Verfahren zur Erzeugung einer derartigen Schicht auf einer Oberfläche einer Dauerform.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.

Auf Grundlage der überaus hohen Korrosion, die gängige metallische Werksstoffe gegenüber Aluminium und anderen Nichteisenmetallen bei typischen Verarbeitungstemperaturen zeigen, müssen Kontaktstellen zwischen dem Nichteisenmetall und der Dauerform mit sogenannten Trennmitteln behandelt sein, damit ein störungsfreier Betrieb möglich ist. Insbesondere aber nicht ausschließlich bei Druckgussprozessen, die durch die Anwendung hoher Temperaturen und Drücke gekennzeichnet sind, werden an die dabei eingesetzten Trennmittel verschiedenste im Folgenden aufgeführte Anforderungen gestellt. So muss das Trennmittel zur Unterstützung des Metallflusses dienen, was zu einer gleichmäßigen Befüllung der Dauerform führt und gleichzeitig dient das Trennmittel zur Verbesserung der Endformbarkeit der gegossenen Teile. Darüber hinaus dient das Trennmittel zur Vermeidung von Rückständen auf der Dauerform, was zu Ungenauigkeiten in der Form führen kann. Während des Eingießens des Werkstoffes in die Dauerform darf keine übermäßige Gasbildung bei der Zersetzung des Trennmittels erfolgen, was zu einer Porosität der Formteile führen würde. Das Trennmittel darf letztendlich auch keine gefährlichen oder toxischen Substanzen enthalten. Je nach Erfüllung dieser Anforderungen wird die Güte des Trennmittels bemessen.Based on the extreme corrosion exhibited by common metallic materials compared to aluminum and other non-ferrous metals at typical processing temperatures, contact points between the non-ferrous metal and the permanent mold must be treated with so-called release agents for trouble-free operation. In particular but not exclusively in die-casting processes, which are characterized by the use of high temperatures and pressures, various requirements set forth below are imposed on the release agents used in the process. Thus, 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. In addition, the release agent serves to avoid residues on the permanent mold, which can lead to inaccuracies in the form. 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.

Ein seit langem bekannter und in Trennmitteln eingesetzter Werkstoff ist Bornitrit (BN), der von seiner Kristallstruktur her ähnlich aufgebaut ist wie Graphit. Wie Graphit weist er gegenüber vielen Substanzen, wie beispielsweise silikatischen Schmelzen oder auch Metallschmelzen eine geringe Benetzbarkeit auf. Daher gibt es viele Untersuchungen zu nicht anhaftenden Schichten auf Basis von Bornitrit, um diese für Gießprozesse zu nutzen. Das Problem bei dieser Nutzung ist jedoch, dass es nicht gelingt, Bornitrit in Substanz auf Formen, insbesondere komplexer Natur, dauerhaft aufzutragen. Ein Verfahren zum dauerhaften Auftragen einer temperaturstabilen, korrosionsbeständigen Formtrennschicht ist in der DE 198 42 660 A1 beschrieben. Hierbei wird ein Bornitrit-Pulver mittels elektrostatischer Beschichtung auf die Oberfläche einer Dauerform aufgebracht.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.

Es wurde ebenfalls versucht, Bindemittel auf anorganischer Basis herzustellen, in die Bornitrit eingebunden ist. In der US 6,051,058 wird die Herstellung von Bornitritschutzschichten mit Dicken von 0,2 bis 0,7 mm auf Feuerfestmaterialien für das kontinuierliche Gießen von Stählen beschrieben. Dabei wird Bornitrit in einer Größenordnung von 20 bis 50 Gew.-% mit Hilfe von Hochtemperaturbindem in Form einer wässrigen Beschichtungslösung auf Basis von Metalloxyden der Gruppe Zr02, Zirkonsilikaten, als AlzO3, SiO2 und Aluminiumphosphaten auf das Feuerfestmaterial gebunden.Attempts have also been made to produce inorganic-based binders in which boron nitride is incorporated. In the US 6,051,058 describes the production of boron nitride protective layers with thicknesses of 0.2 to 0.7 mm on refractory materials for the continuous casting of steels. In this case, boron nitride in the order of 20 to 50 wt .-% by means of Hochtemperaturbindem in the form of an aqueous coating solution based on metal oxides of the group Zr0 2 , zirconium silicates, as Al z O 3 , SiO 2 and aluminum phosphates bonded to the refractory material.

Um den Verschleiß und die Korrosion von Werkstoffen zu unterdrücken, ist aus der DE 101 24 434 A1 eine Verschleißschutzschicht bekannt, in der Funktionswerkstoffe in einer Bindermatrix eingebunden sind. Diese sogenannte Funktionsbeschichtung besteht dabei aus einer anorganischen Matrixphase, die zumindest weitgehend aus einem Phosphat besteht, und einem darin eingebetteten Funktionswerkstoff, der beispielsweise ein Metall, Graphit, ein Hartstoff, ein Trockenschmierstoff, ein Aluminiumoxid, ein Siliziumkarbid, etc. sein kann. Beschrieben ist ebenfalls ein Verfahren zur Herstellung dieser Funktionsbeschichtung, wobei in eine flüssige Komponente, die beispielsweise Wasser sein kann, ein Funktionswerkstoff in Pulverform gelöst und zur Erzeugung eines Phosphates mit Phosphorsäure versetzt wird. Eine derartig zusammengesetzte Matrixlösung mit der flüssigen Komponente und dem Phosphat kann auf Grund ihrer Konsistenz auch als Gel bezeichnet werden. Nach dem Beschichten eines Werkstoffes mit dieser Matrixlösung erfährt der Werkstoff eine Wärmebehandlung, so dass sich eine festhaftende Funktionsbeschichtung auf dem Grundwerkstoff ausbildet.To suppress the wear and corrosion of materials, is from the DE 101 24 434 A1 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. Described is also a method for producing this functional coating, wherein dissolved in 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. 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.

Des Weiteren ist aus der US 3,770,465 eine Formschlichte bekannt, welche aus Wasser und Kaliumzirkonfluorid sowie einem Binder aus Phenolharz oder Zirkonstaub oder ähnlichem in trockener Form besteht. Hierdurch sollen glatte Oberflächen auf den Formen entstehen, was ein Eindringen von Metall beim Gießprozess verhindern soll.Furthermore, from the US 3,770,465 a mold size known, which consists of water and potassium zirconium fluoride and a binder of phenolic or zirconium dust or the like in a dry form. This is to create smooth surfaces on the molds, which should prevent metal from penetrating during the casting process.

Die Aufgabe der vorliegenden Erfindung ist es, eine langzeitstabile Schicht auf einer metallischen, eisenhaltigen Dauerform zu entwickeln, die eine chemische Bindung mit dem Grundwerkstoff der Dauerform eingeht und somit den Anforderungen an ein Trennmittel genügt oder sogar über diese Anforderungen hinaus geht, indem Gießfehler durch die Bildung von Oxidhäuten beim Gießprozess vermieden werden. Darüber hinaus ist es Aufgabe der Erfindung ein Trennmittel zur Herstellung einer derartigen Schicht bereitzustellen, das kostengünstig herzustellen und einfach und ohne Vorrichtungsaufwand zu applizieren ist. Eine weitere Aufgabe der Erfindung ist es, ein Verfahren bereit zu stellen, das in der Lage ist eine derartige Schicht zu erzeugen und mittels dem Beschädigungen an der Schicht leicht ausheilbar sind.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 Dauerform 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.

Die erfindungsgemäße Aufgabe in Bezug auf eine Beschichtung einer Dauerform wird dahingehend gelöst, dass auf mindestens einer Oberfläche der Dauerform eine Schicht bestehend aus

  • chemisch mit einem Grundwerkstoff der Dauerform gebundenem Eisenfluorid,
  • Strukturteilen einer oder mehrerer der Verbindungen Al2O3, SiO2, TiO2 und ZurO2 in einer Fraktion von 80nm bis 200nm und
  • einem die Strukturteile zumindest bereichsweise umschließenden Polymer aus polymerisiertem Zirkoniumfluorid vorhanden ist.
The object according to the invention with respect to a coating of a permanent mold is achieved in that on at least one surface of the permanent mold a layer consisting of
  • chemically bound with a base material of the permanent form iron fluoride,
  • Structural parts of one or more of the compounds Al 2 O 3 , SiO 2 , TiO 2 and ZurO 2 in a fraction of 80nm to 200nm and
  • a polymer of polymerized zirconium fluoride is at least partially enclosing the structural parts present.

In bevorzugten Ausführungsformen der Erfindung enthält die Schicht zusätzlich:

  • Primärteile der Form Al2O3, SiO2, TiO2, ZnO, ZrO2, CeO2 in einer Fraktion von 2nm bis 80nm, und/oder
  • Gleitteile der Form Bornitrit, in einer Fraktion von 2µm bis 15µm und/oder
  • Glimmer, als silikatisches Mineral.
In preferred embodiments of the invention, the layer additionally contains:
  • Primary parts of the form Al 2 O 3 , SiO 2 , TiO 2 , ZnO, ZrO 2 , CeO 2 in a fraction of 2nm to 80nm, and / or
  • Slide parts of the form Bornitrit, in a fraction of 2μm to 15μm and / or
  • Mica, as a silicate mineral.

Durch die erfindungsgemäße Schicht auf der metallischen Dauerform werden die Anforderungen an ein Trennmittel, in Form einer langzeitstabilen Schicht besonders gut erfüllt. So wird der Metallfluss dahingehend unterstützt, dass durch die aus der Schicht herausstehenden Strukturteile die Oxidhaut des Aluminiumwerkstoffes aufgebrochen wird und sich der flüssige Aluminiumwerkstoff unterhalb der Oxidschicht sehr leicht in der Dauerform verteilen kann. Die Schicht bietet somit optimale Bedingungen für das Befüllen der Dauerform. Die Gleitteile der Form Bornitrit (BN) dienen als Gleitebene für das flüssige oder fließfähige Aluminium und unterstützen somit den Metallfluss, sie dienen darüber hinaus gleichzeitig zur Verbesserung der Endformbarkeit der gegossenen Bauteile.Due to the layer according to the invention on the permanent metallic form, the requirements for a release agent in the form of a long-term stable layer are particularly well met. Thus, 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 Endformbarkeit of the cast components.

Auf der Oberfläche der Dauerform wird eine festhaftende Schicht gebildet, wobei der feste Verbund durch die chemische Bindung der Fluoride mit dem Eisen des Grundwerkstoffes der Dauerform erzeugt wird. Durch diese Art der festen Bindung der Schicht mit dem Grundwerkstoff der Dauerform wird vermieden, dass Rückstände auf der Dauerform haften bleiben, was zu Maßungenauigkeiten führen könnte. Ein weiterer Vorteil der erfindungsgemäßen Schicht ist es, dass die Schicht bei höheren Temperaturen zu einer vermehrten Polymerisation angeregt wird. Hierdurch bilden sich längere Polymere, die einerseits die Haftung und den Zusammenhalt erhöhen und andererseits die Elastizität der Schicht erhöhen. Die langzeitstabile und festhaftende Schicht ist somit bei höheren Temperaturen, wie sie während des Befüllens der Dauerform auftreten, äußerst elastisch und kann den Formänderungen der Dauerform elastisch und somit vorteilhafterweise ohne eine Beschädigung der Schicht folgen.On the surface of the permanent mold 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.

In Bezug auf das Trennmittel wird die erfindungsgemäße Aufgabe dahin gehend gelöst, dass das Trennmittel aus einem vollständig entsalzten Wasser gebildet ist und die folgenden Bestandteile enthält:

  • eine oder mehrere der Verbindungen Natriumlauge, Kaliumlauge und Aluminiumchlorid,
  • einen Binder aus Zirkoniumfluorid, bevorzugt in der Form H2ZrF6,
  • einen Anteil an Strukturteilen einer oder mehrerer der Verbindungen Al2O3, SiO2, TiO2 und ZrO2 in einer Fraktion von 80nm bis 200nm und
  • ein organisches Dispergiermittel, vorzugsweise Gelatine.
With respect to the release agent, the object according to the invention is achieved in that the release agent is formed from a completely desalted water and contains the following constituents:
  • one or more of the compounds sodium lye, potassium lye and aluminum chloride,
  • a binder of zirconium fluoride, preferably in the form H 2 ZrF 6 ,
  • a proportion of structural parts of one or more of the compounds Al 2 O 3 , SiO 2 , TiO 2 and ZrO 2 in a fraction of 80nm to 200nm and
  • an organic dispersant, preferably gelatin.

In bevorzugten Ausführungsformen der Erfindung enthält das Trennmittel zusätzlich:

  • einen Anteil an Primärteilen der Form Al2O3, SiO2, TiO2, ZnO, ZrO2, CeO in einer Fraktion von 1nm bis 10nm und/oder
  • einen Anteil an Gleitteilen der Form BN und/oder Magnesiumaluminiumsilikat und/oder Molybdändisulfid, in einer Fraktion von 2µm bis 15µm und/oder
  • Glimmer.
In preferred embodiments of the invention, the release agent additionally contains:
  • a proportion of primary parts of the form Al 2 O 3 , SiO 2 , TiO 2 , ZnO, ZrO 2 , CeO in a fraction of 1 nm to 10 nm and / or
  • a proportion of sliding parts of the form BN and / or magnesium aluminum silicate and / or molybdenum disulfide, in a fraction of 2μm to 15μm and / or
  • Mica.

Das erfindungsgemäße Trennmittel bietet zum einem den Vorteil, dass es auf Grundlage von vollentsalztem Wasser kostengünstig herzustellen ist und andererseits auf Grund seiner Viskosität einfach auf das Werkzeug zu applizieren ist. im einfachsten Fall kann das Trennmittel auf die Dauerform aufgesprüht werden. Darüber hinaus entspricht das Trennmittel den Anforderungen an ein Trennmittel dahingehend, dass keine toxischen Substanzen enthalten sind, die nur mit hohen Kosten entsorgt werden können.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.

Die erfindungsgemäße Aufgabe in Bezug auf das Verfahren zur Erzeugung einer Schicht wird dahingehend gelöst, dass die Oberfläche zuerst mit dem Trennmittel, gemäß einen der Ansprüche 6 bis 13, beaufschlagt wird und dass anschließend die Dauerform auf eine Temperatur von mindestens 200°C erwärmt wird. Durch diese Erwärmung geht das Fluorid eine chemische Bindung mit dem Eisen des Grundwerkstoffes ein und das Zirkoniumfluorid bildet Polymere, die eine festhaftende Schicht auf der Oberfläche der Dauerform bilden. Vorteilhaft hierbei ist, dass das Trennmittel, das aus einem vollständig entsalztem Wasser besteht, bei dieser Temperatur bereits vollständig aus der Schicht ausgedampft ist und es somit zu keiner oder nur sehr geringen Gasbildung beim Befüllen der Dauerform kommt. Darüber hinaus wird die Polymerisation bei der Erhöhung der Temperatur noch unterstützt, so dass wie oben beschrieben ein weiterer vorteilhafter Effekt der Schicht erzeugt wird. Der Einsatz von Gelatine ist dabei besonders vorteilhaft, da hierdurch selbstständig Nanopartikel gebildet werden.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. As a result of this heating, 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. In addition, 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.

Sollte es darüber hinaus zu einer Beschädigung der Schicht kommen, so ist die Schicht sehr leicht ausheilbar, da nach einem erneuten Applizieren der Dauerform mit dem Trennmittel Fehlstellen in der Schicht unmittelbar ausgehellt werden. Dabei wird neues Eisenfluorid gebildet und durch die Temperatur der Dauerform polymerisiert das Zirkoniumfluorid, so dass die Schicht vollständig ausheilt.If, in addition, the layer is damaged, 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. In this case, new iron fluoride is formed and by the temperature of the permanent form zirconium fluoride polymerizes, so that the layer completely heals.

Auf der Oberfläche, die bevorzugt natürlich die Seite der Dauerform ist, die dem herzustellenden Gussteil entspricht, wird eine Schicht gebildet, die in einer Dicke von ca. 1 bis 80 µm aufweist, bevorzugt sind Schichtdicken zwischen 30 und 50 µm, was aber wiederum vom Einsatzfall abhängig ist. Die Schichtdicke ist abhängig vom Einsatzfall, dass heißt vom Gießverfahren, wobei beim Druckguss die dünnsten und beim Niederdruck die dicksten Schichten verwendet werden. Beim Druckguss, werden die dünnsten Schichten aufgetragen, da hier ein guter Wärmeübergang zur Dauerform bewusst eingestellt wird, um eine schnelle Erstarrung des Gießteils zu ermöglichen. Bei dem kombinierten sogenannten Squeeze-Casting-Verfahren wird eine mittlere Dicke eingestellt, da hierbei die Gießform langsam gefüllt und anschließend mit einem hohen Druck beaufschlagt wird. Hierbei ist somit ein geringerer Wärmeübergang zur Dauerform nützlich. Beim Niederdruckgießen hingegen sind dicke Schichten vorteilhaft, da hier die Form relativ langsam befüllt wird und ein langsames Abkühlen des Gussteils von Vorteil ist. Darüber hinaus ist die erfindungsgemäße, mit einer Beschichtung versehene Dauerform natürlich auch für das Schwerkraftgießen einsetzbar.On the surface, which is of course preferably the side of the permanent mold corresponding to the casting to be produced, 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. In this case, a lower heat transfer to the permanent form is thus useful. In low-pressure casting, on the other hand, thick layers are advantageous, since here the mold is filled relatively slowly and slow cooling of the casting is advantageous. In addition, the permanent mold provided with a coating according to the invention can of course also be used for gravity casting.

Die auf der Oberfläche der Dauerform vorhandene Schicht ist chemisch mittels des Eisenfluorids mit dem Grundwerkstoff verbunden. Das Eisenfluorid wirkt somit als Haftmittel zwischen Schicht und Grundwerkstoff. Die Strukturteile der Form Al2O3 und/oder SiO2 und/oder TiO2 und/oder ZrO2 besitzen eine Größe von etwa 80nm, bis 200nm und verhaken sich gegeneinander und bilden eine Schicht auf dem Grundwerkstoff. Hierbei ist der Begriff Strukturteile gezielt ausgewählt, da bevorzugt Teilchen eingesetzt werden, die nicht glatt sind sondern eine strukturierte Oberfläche aufweisen. In die Lücken zwischen den Strukturteilen lagern sich die Primärteile der Form Al2O3 und/oder SiO2 und/oder Zinkoxid und/oder Titandioxid und/oder Zirkoniumdioxid und/oder Ceroxid, die in einer Größe von 1nm bis 10nm vorliegen, bevorzugt und sehr leicht ein. Die sehr viel größeren Gleitteile des Bornitrits liegen zwischen den Strukturteilen in der Schicht und werden durch den Verbund aus Strukturteilen mit Polymeren gehalten. Die so aufgebaute Schicht hat bereits auf Grund seines fraktilen Aufbaus eine in sich verklammernde Wirkung, die wesentliche Bindung zwischen dem Eisenfluorid und den Strukturteilen, den Primärteilen und den Gleitteilen wird aber durch das polymerisierte Zirkoniumfluorid geschaffen. Die Ketten der Polymere stellen den Zusammenhalt zwischen dem chemisch gebundenen Eisenfluorid, den Strukturteilen, den Primärteilen und den Gleitteilen her. Je stärker die Dauerform erhitzt wird und somit ebenfalls die Schicht, je länger werden die Polymerketten, so dass bei steigender Temperatur die Elastizität der Schicht zunimmt. Die erfindungsgemäß eingesetzten Polymere polymerisieren bei ca. 200°C und besitzen eine Verglasungstemperatur von ca. 830°C. Das flüssige Aluminium besitzt eine Temperatur von ca. 730°C und reicht somit nicht an die Verglasungstemperatur der Polymere heran. Es ist somit ein äußerst stabiles, für das Gießen von Aluminium-Werkstoffen sehr gut geeignetes System als Schichtaufbau geschaffen.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. In this case, the term structural parts is selected specifically, since particles are preferably used which are not smooth but have a structured surface. In the gaps between the structural parts, 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 more strongly the permanent mold is heated and thus likewise the layer, the longer the polymer chains become, so that with increasing temperature the elasticity of the layer increases. 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.

Die Eisenfluoride dienen als Haftmittel zum Grundwerkstoff der Dauerform und die Primärteile werden vorteilhafterweise dazu eingesetzt, die Lücken zwischen den Strukturtellen zu schließen, um somit eine sehr glatte Oberfläche zu erzeugen. Ein Anhaften des flüssigen Gießwerkstoffes ist somit nahezu fast unmöglich. Die Strukturteile liegen in einer Größe von 80nm bis 200nm vor und stehen als Kanten aus der Schicht heraus. Vorteilhafterweise reißen die an ihrer Oberfläche stark strukturierten Strukturteile Risse in die Oxidschicht des flüssigen Aluminiums und zerreiben die Oxidhaut, so dass die Oxidhaut in kleinste Teile zerrieben wird und somit nicht als Gitterfehler im Gefügeaufbau des Gussteils vorliegen. Ein Vorteil der erfindungsgemäß eingesetzten Strukturteile ist somit, dass die Oxidhaut zerstört und zerkleinert wird.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. Advantageously, 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.

Die Gleitteile die in der Form als Bornitrit vorliegen, besitzen eine sehr viel größere Größe als die Primär- und die Strukturteile. Erfindungsgemäß bilden die Strukturteile mit einem Gewichtsprozentanteil von bis zu 10 % im flüssigen Trennmittel den größten Teil der Schicht. Die Primärteile dienen als Füllmittel für die Zwischenräume und dienen somit der Glättung der Schicht. Die Gleitteile, in einem Gewichtsanteil von bis zu 5 % vorliegend, sind fein verteilt in die Strukturteile eingelagert und treten ebenfalls an der Oberfläche der Schicht heraus. Auf Grund der Anzahl der Gleitteile, bilden diese nicht die größte Oberfläche der Schicht sondern liegen feinst verteilt vor, so dass sie als Gleitmittel zum einem beim Gießen aber vornehmlich zum Entformen der Dauerform und zur Entnahme des Gussteils dienen. Das Entformen wird durch den Einsatz der erfindungsgemäßen Schicht in vorteilhafterweise erleichtert, da zum einem durch die Strukturteile und die glättend wirkenden Primärteile eine sehr glatte Oberfläche an der Schicht vorhanden ist und gleichzeitig durch die Gleitteile ein Schmiermittel zur Verfügung gestellt wird.The sliding parts, which are in the form of boron nitride, are much larger in size than the primary and structural parts. According to the invention 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.

Die Versuche haben gezeigt, dass durch die Zugabe von Natriumlauge und/oder Kaliumlauge und/oder Aluminiumchlorid und die Einstellung eines pH-Wertes von 4 bis 5 eine optimale Bildung der Schicht erzeugt wird.The experiments have shown that by the addition of sodium hydroxide and / or potassium hydroxide and / or aluminum chloride and the adjustment of a pH of 4 to 5 optimum formation of the layer is produced.

Erfindungsgemäß wird die kalte Dauerform mit dem Trennmittel beaufschlagt, in dem das Trennmittel aufgesprüht und die Dauerform erhitzt wird. Ab einer Temperatur von ca.200°C polymerisiert das Zirkoniumfluorid und es kommt zu einer Bildung einer langzeitstabilen Schicht auf der Oberfläche der Dauerform. Eine übliche Temperatur zum Vorheizen beim Druckgießen ist eine Temperatur zwischen 220°C und 280°C, so dass hier eine optimale Temperatur zur Polymerisation des Trennmittels vorhanden ist. Beim Niederdruckguss und Squeeze-Casting liegen die Vorheiztemperaturen noch über 300°C, so dass auch hier eine Ausbildung einer Schicht gewährleistet ist. Das flüssige Metall mit einer Temperatur von ca. 720°C bis 730°C beim Gießen von Aluminium liegt unterhalb der Glasübergangstemperatur. Aber auch das Thixocasting liegt oberhalb von 200°C und somit ist der Einsatz der erfindungsgemäßen Schicht bei diesem Verfahren ebenso vorstellbar.According to the cold permanent form is applied to the release agent in which the release agent is sprayed and the permanent mold is heated. From a temperature of about 200 ° C., 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. In low-pressure casting and squeeze casting, 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.

Claims (15)

  1. A metallic, iron-containing permanent mold, particularly a permanent mold made of steel, which can be provided with a liquid or free-flowing aluminum material,
    characterized in that
    on at least one surface of the permanent mold there is a layer comprising:
    - iron fluoride bound chemically to the base material of the permanent mold;
    - structural parts in the form of one or more of the compounds Al203, SiO2, TiO2 and ZrO2 in a fraction of 80 nm to 200 nm; and
    - a polymer of polymerized zirconium fluoride, surrounding the structural parts at least partially.
  2. The permanent mold according to claim 1, characterized in that sliding parts in the form of boron nitrite and/or magnesium aluminum silicate and/or molybdenum disulfide are present in the layer in a fraction of 2 µm to 15 µm.
  3. The permanent mold according to one or both of claims 1 and 2, characterized in that primary parts in the form of Al203, SiO2, ZnO, ZrO2, TiO2, and CeO are present in the layer in a fraction of 2 nm to 80 nm, wherein the primary parts are embedded in the gaps between the structural parts.
  4. The permanent mold according to one of claims 1 to 3, characterized in that the layer is present on the surface in a thickness of 1 µm to 80 µm, preferably in a thickness of 25 µm to 60 µm.
  5. The permanent mold according to one or more of claims 1 to 4, characterized in that the permanent mold is a permanent mold for a pressure casting, low-pressure casting, gravity casting, or squeeze casting method.
  6. A mold release agent for preparing a layer on a permanent mold,
    characterized in that
    the parting agent is formed of deionized water and comprises the following components:
    - one or more of the compounds sodium hydroxide solution, potassium hydroxide solution and aluminum chloride,
    - a binder of zirconium fluoride,
    - an amount of structural parts in the form of one or more of the compounds Al203, SiO2, TiO2 and ZrO2 in a fraction of 80 nm to 200 nm is present, and
    - an organic dispersant, preferably gelatin.
  7. The mold release agent according to claim 6, characterized in that an amount of sliding parts in the form of boron nitrite and/or magnesium aluminum silicate and/or molybdenum disulfide is present in the mold release agent in a fraction of 2 µm to 15 µm.
  8. The mold release agent according to one or both of claims 6 and 7, characterized in that an amount of primary parts in the form of Al203, SiO2, ZnO, ZrO2, CeO, TiO" and/or mica is present in the mold release agent in a fraction of 2 nm to 80 nm.
  9. The mold release agent according to one or more of claims 6 to 8, characterized in that a pH of 4 to 5 is established in the mold release agent.
  10. The mold release agent according to one or more of claims 6 to 9, characterized in that the amount of the binder in the mold release agent is less than or equal to 5% by weight.
  11. The mold release agent according to one or more of claims 6 to 10, characterized in that the amount of the structural parts in the mold release agent is less than or equal to 10% by weight.
  12. The mold release agent according to one or more of claims 6 to 11, characterized in that the amount of primary parts in the mold release agent is less than or equal to 3% by weight and is preferably between 1% by weight and 3% by weight.
  13. The mold release agent according to one or more of claims 6 to 12, characterized in that the amount of sliding parts in the mold release agent is less than or equal to 5% by weight.
  14. A method for creating a layer on a metallic, iron-containing surface of a permanent mold by a mold release agent of one of the preceding claims, characterized in that
    the surface is first provided with a mold release agent, and the permanent mold is then heated to a temperature of at least 200° C, so that chemical binding of a fluoride with an iron of the base material and polymerization of the binder occur.
  15. The method according to claim 14, characterized in that damage in the layer is healed by a repeated application of the mold release agent to the permanent mold.
EP07722819.5A 2006-03-07 2007-02-15 Mold release layer for casting nonferrous metals Not-in-force EP1993755B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006010876A DE102006010876A1 (en) 2006-03-07 2006-03-07 Mold release layer for casting non-ferrous metals
PCT/EP2007/001300 WO2007101528A1 (en) 2006-03-07 2007-02-15 Mold release layer for casting nonferrous metals

Publications (2)

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

Family

ID=38109514

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07722819.5A Not-in-force EP1993755B1 (en) 2006-03-07 2007-02-15 Mold release layer for casting nonferrous metals

Country Status (8)

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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006010875A1 (en) * 2006-03-07 2007-09-13 Ks Aluminium-Technologie Ag Coating of a thermally and erosively loaded functional component
DE102013020872B4 (en) 2013-12-11 2016-03-03 Audi Ag Process for producing a fiber-reinforced plastic component with a hollow structure
CN106270370B (en) * 2016-08-10 2019-02-19 中原内配集团股份有限公司 A kind of needle prick shape cylinder jacket and preparation method thereof
WO2018028125A1 (en) 2016-08-10 2018-02-15 中原内配集团股份有限公司 Needle-shaped cylinder liner and preparation method therefor, and coating liquid for preparing needle-shaped cylinder liner
JP6434946B2 (en) * 2016-09-29 2018-12-05 トヨタ自動車株式会社 Nitride repair method
CN116199510B (en) * 2023-01-03 2024-03-15 三祥新材股份有限公司 Mold demolding method in production process of fused zirconia
DE102023103887A1 (en) 2023-02-16 2024-08-22 Audi Aktiengesellschaft Method for producing a die-cast component, die-cast component and motor vehicle

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1433969B2 (en) * 1963-11-19 1973-02-08 Larsson, Rune, Sandviken (Schweden) FLUORINE PROTECTIVE LAYER FOR CASTING FORMS AND THE PROCESS FOR THEIR PRODUCTION
US3770465A (en) * 1971-07-19 1973-11-06 Exoment Inc Mold wash composition
US3727666A (en) * 1971-08-16 1973-04-17 Howmet Corp Method of casting using a mold having a refractory coating thereon
US4454050A (en) * 1983-03-21 1984-06-12 Pennwalt Corporation Aqueous release agent and lubricant
JPS62248536A (en) * 1986-04-21 1987-10-29 Daido Steel Co Ltd Casting method and casting apparatus
TW265327B (en) * 1990-05-14 1995-12-11 Minteq Internat Inc
JP3066812B2 (en) * 1991-10-09 2000-07-17 黒崎播磨株式会社 Low melting metal casting tool with two or more coatings
JPH08300361A (en) * 1995-05-10 1996-11-19 Olympus Optical Co Ltd Mold for molding resin
FR2755384B1 (en) * 1996-11-06 1998-11-27 Usinor Sacilor PROTECTIVE COATING FOR ELEMENTS OF REFRACTORY MATERIAL OF A CONTINUOUS CASTING LINGOTIERE OF METALS, AND ELEMENTS OF REFRACTORY MATERIAL PROTECTED USING THIS COATING
DE19842660A1 (en) 1998-09-17 2000-03-30 Kempten Elektroschmelz Gmbh Process for coating a surface with a release agent
US6474397B1 (en) * 2000-01-20 2002-11-05 Alcoa Inc. Fluxing agent for metal cast joining
JP2001232443A (en) * 2000-02-21 2001-08-28 Yuji Sengoku Coating structure for surface treatment of die
DE10124434A1 (en) 2001-05-18 2002-11-28 Bosch Gmbh Robert Functional coating and process for its production, in particular for wear protection, corrosion protection or for temperature insulation
DE10326815A1 (en) * 2003-06-13 2004-12-30 Institut für Neue Materialien Gemeinnützige GmbH Anti-adhesive high-temperature coatings
US20050043189A1 (en) * 2003-08-18 2005-02-24 Stewart Patricia A. Lubricant for improved surface quality of cast aluminum and method

Also Published As

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

Similar Documents

Publication Publication Date Title
WO2007028615A2 (en) Mold-release layer for use in the casting of nonferrous metals
DE102005042473B4 (en) A coating agent for producing a protective layer on a ceramic surface of a casting tool, a ceramic surface casting tool, a method for producing a protective layer on a ceramic surface and a method for curing a damage of the protective layer
EP1993755B1 (en) Mold release layer for casting nonferrous metals
DE3120582C2 (en) Mould with heat-insulating protective layer
EP2014392B1 (en) Moulding material mixture, moulded blank for moulding purposes and method for producing a moulded blank
DE1758845C3 (en) Process for the production of precision casting molds for reactive metals
DE112006003537B4 (en) Method of making a sputtering target assembly
EP3253513A1 (en) Method for producing a component from a superalloy by way of a powder-bed-based additive production method and component made from a superalloy
DE102007059771A1 (en) Cylinder bush or cylinder liner made of gray iron- or aluminum alloy for casting in a light metal alloy on the basis of aluminum or aluminum/magnesium, comprises a conditioning coating for casting
WO2006058664A2 (en) Use of poorly soluble salts in combination with liquid glass for producing moulds and cores used in casting methods
WO2009007093A2 (en) Coating system for the protection of casting moulds
WO2008025448A1 (en) Size for production of a bn-containing coating, method for production thereof coated body production and use thereof
DE112013004948T5 (en) Precision casting mold and process for its production
WO1995005490A1 (en) Molten mass treating agent, its production and use
EP2723916B1 (en) Casting component, and method for the application of an anticorrosive layer
DE2604754A1 (en) FRICTION MATERIAL
WO2005046911A1 (en) Method for producing metal matrix composite materials
DE102005029039B4 (en) Production process for mold with non-stick coating
EP1674756B1 (en) Braking system for a vehicle, in particular a motor vehicle
DE19918002C1 (en) Process for casting a light metal cylinder head used in engines uses two light metal alloys
DE19535444C2 (en) Process for the powder metallurgical manufacture of articles and articles produced in this way
WO2006034850A1 (en) Method for production of cast pieces and insert for cast pieces
DE102016219114A1 (en) Particles of a refractory ceramic material for influencing the damage tolerance of high-temperature materials, and process for their preparation
DE102021116044A1 (en) Process for producing a die-cast component
DE102023103887A1 (en) Method for producing a die-cast component, die-cast component and motor vehicle

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17P Request for examination filed

Effective date: 20080926

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: KS ALUMINIUM-TECHNOLOGIE GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: KS ALUMINIUM-TECHNOLOGIE GMBH

Owner name: GELITA AG

17Q First examination report despatched

Effective date: 20100528

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502007012049

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: B22C0003000000

Ipc: B22D0017220000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/74 20060101ALI20130312BHEP

Ipc: C23C 22/34 20060101ALI20130312BHEP

Ipc: C23C 22/73 20060101ALI20130312BHEP

Ipc: B22D 17/22 20060101AFI20130312BHEP

INTG Intention to grant announced

Effective date: 20130418

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 621851

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502007012049

Country of ref document: DE

Effective date: 20130912

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130717

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130619

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131117

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131118

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131018

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131028

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

26N No opposition filed

Effective date: 20140422

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502007012049

Country of ref document: DE

Effective date: 20140422

BERE Be: lapsed

Owner name: KS ALUMINIUM-TECHNOLOGIE G.M.B.H.

Effective date: 20140228

Owner name: GELITA A.G.

Effective date: 20140228

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140215

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20140215

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

Ref country code: LI

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

Effective date: 20140228

Ref country code: CH

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

Effective date: 20140228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20141031

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: FR

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

Effective date: 20140228

Ref country code: GB

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

Effective date: 20140215

Ref country code: BE

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

Effective date: 20140228

Ref country code: IE

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

Effective date: 20140215

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 621851

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140215

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

Ref country code: AT

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

Effective date: 20140215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502007012049

Country of ref document: DE

Representative=s name: PATENTANWAELTE TER SMITTEN EBERLEIN RUETTEN PA, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 502007012049

Country of ref document: DE

Owner name: GELITA AG, DE

Free format text: FORMER OWNERS: GELITA AG, 69412 EBERBACH, DE; KS ALUMINIUM-TECHNOLOGIE GMBH, 74172 NECKARSULM, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 502007012049

Country of ref document: DE

Owner name: KS HUAYU ALUTECH GMBH, DE

Free format text: FORMER OWNERS: GELITA AG, 69412 EBERBACH, DE; KS ALUMINIUM-TECHNOLOGIE GMBH, 74172 NECKARSULM, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 502007012049

Country of ref document: DE

Representative=s name: PATENTANWAELTE TER SMITTEN EBERLEIN-VAN HOOF R, DE

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

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20070215

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130717

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

Ref country code: DE

Payment date: 20180221

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502007012049

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20190903