EP2723916A2

EP2723916A2 - Casting component, and method for the application of an anticorrosive layer

Info

Publication number: EP2723916A2
Application number: EP12729600.2A
Authority: EP
Inventors: Norbert Erhard; Helmar Dannenmann; Jürgen KURZ; Andreas Sydlo; Daniel Gerner
Original assignee: Oskar Frech GmbH and Co KG
Current assignee: Oskar Frech GmbH and Co KG
Priority date: 2011-06-24
Filing date: 2012-06-22
Publication date: 2014-04-30
Anticipated expiration: 2032-06-22
Also published as: CN103930597A; WO2012175668A3; TR201905070T4; RU2014101456A; US20140193635A1; KR102019176B1; WO2012175668A2; EP2723916B1; US10766064B2; KR20140043112A; JP2014519985A; CN103930597B; RU2578301C2; ES2719125T3; PL2723916T3; JP6073305B2; BR112013032678A2; BR112013032678B1; MX2013014924A; DE102011078066A1

Abstract

The invention relates to a casting component for a device used to cast a molten metal. Said casting component has a metal main member (2) and a molten metal-contacting surface area (9) which is exposed to the molten metal during the casting process. The invention also relates to a method for applying an anticorrosive layer to a substrate, which can in particular be a casting component. In the casting component of the invention, the metal main member is provided with an anticorrosive layer (3) in the molten metal-contacting surface area, said anticorrosive layer (3) being resistant to the molten metal and being composed of a group of substances consisting of borides, nitrides, and carbides of the transition metals and of the alloys thereof and of boron and silicon, as well as of Al₂O₃, microparticles and/or nanoparticles of one or more substances being used. Use for casting receptacles and other components of aluminum die-casting machines, for example.

Description

Casting component and method for applying a

Corrosion protection layer

The invention relates to a casting component for a device for casting or handling a molten metal, wherein the component has a metallic base body and a surface region which is exposed to molten metal in the casting operation, and to a method for applying a corrosion protection layer to a substrate which may in particular be the casting-technical component.

Such casting components are in the metal casting in many forms in use, for example, as Gießgarnituren, casting containers, melting furnaces, melt delivery units and molds and parts of these Metallgießkomponenten. In most cases, a steel material is used for the base body, since such components have a good cost / benefit ratio.

However, it has been found that casting components made of steel in areas in which they are used in the casting operation with the hot metal come into contact, are chemically attacked by the liquid molten metal, ie subject to corrosion. Thus, for example, a noticeable corrosion attack by aluminum melts during aluminum die casting is observed on steel surfaces of casting components coming into contact with it. As a remedy, it is known for casting piston / casting cylinder units of metal die casting machines to manufacture the casting piston and the casting cylinder completely from a ceramic material or from a sintered material, eg from sintered titanium boride (TiB ₂ ). However, the mechanical strength, heat resistance and impact resistance remained unsatisfactory. As a remedy in the published patent application DE 2 364 809 it is proposed to manufacture the casting piston and the casting cylinder as a composite sintered component from a mixture of two or more substances from the substance group, which consists of the carbides, borides and nitrides. In particular, a specific mixture of boron carbide (B ₄ C) with one or more of TiB ₂ , zirconium diboride (ZiB ₂ ) and boron nitride (BN) is given.

In US Pat. No. 4,556,098, this and other sintered materials under investigation are further described as unsatisfactory and, alternatively, a hot-pressed, high-density, ultra-hard silicon nitride or sialon material is proposed for the casting cylinder and the casting piston. For a crucible made of cast iron, a protective coating against corrosion and oxidation of Ca, Al2O3 or other oxides such as ΑΙ2Ο3-ΤΊΟ2 or TiB ₂ , ZaB ₂ , CaB ₂ or other pure or mixed borides or AIN, Si3N ₄ , BN, sialons or specified other nitrides, which is applied for example from an emulsion or by flame spraying. For conical plugs for closing access holes for the riser channel and other parts of a casting, the production of such corrosion and erosion resistant materials is also proposed. For parts of the mold that are exposed to molten metal only at lower temperatures, For example, a coating of a dense material of Si ₃ N ₄ , AlN, Sialon, BN, graphite or pyrolytic carbon or alloys thereof is proposed.

The invention is based on the technical problem of providing a casting component of the aforementioned type and a method for applying a corrosion layer on a substrate, which may in particular be a casting component, based, with the casting component can be produced with relatively little effort and shows a high corrosion resistance against molten metal casting melts and with the method a corrosion protection layer with high corrosion resistance, in particular compared to hot molten metal can be applied comparatively easily and with good layer homogeneity even in hard to reach places.

The invention solves this problem by providing a casting component having the features of claim 1 and a corrosion protection layer application method having the features of claim 11.

In the casting-technical component according to the invention, the metallic base body in the melt-contact surface region in which it is exposed to the molten metal in the casting operation is provided with a corrosion-resistant layer which is resistant to the molten metal and which characteristically comprises one or more substances from one or more of the microparticles and / or nanoparticles Substance group is formed, which consists of borides, nitrides and carbides of the transition metals and their alloys and of boron and silicon and of Al2O3. Investigations have shown that a casting component equipped with this special corrosion protection layer has an unexpectedly good corrosion resistance against the contact with hot, reactivating molten metal shows, especially against aluminum smelting. As an explanation, the presence of the one or more anti-corrosive substances in the form of micro- and / or nanoparticles in the layer is primarily assumed. In particular, studies have shown that casting components coated in this way have very high corrosion resistance to aluminum melts and correspondingly long service life, which may be superior to similar components made entirely of a steel material or a ceramic material, or those in a conventional manner with a corrosion protection layer without micro - And / or nanoparticles are provided in the layer structure, even if the same substances are used for the anti-corrosion layer.

Due to the special corrosion protection layer can be used for the main body of the casting component according to a development of the invention, a common steel material, which in the present case also stainless steel material is to be understood. This allows a simple manufacture of the component compared to the use of ceramic materials. In addition, existing components with such a body made of steel material can be easily retrofitted with the corrosion protection layer. The well-known good mechanical properties of steel for the casting-technical component are retained.

In one development of the invention, the micro- and / or nanoparticles have an average particle size between 50 nm and 50 μm. In particular, average particle sizes between 100 nm and 30 μm, and more particularly between 150 nm and 30 μm, prove to be very advantageous for the corrosion protection layer designed for resistance to hot, reactive molten metals. In one development of the invention, the corrosion protection layer contains at least microparticles and / or nanoparticles of TiB ₂ . On the basis of these TiB ₂ particles built corrosion protection layers, which optionally may additionally contain micro- and / or nanoparticles of one or more other substances, show a very high corrosion resistance to corrosion by hot Al-melting.

In an advantageous embodiment, the anticorrosion layer is a sol-gel layer, i. a layer applied by a sol-gel process, wherein the micro- and / or nanoparticles act as a filler, with which the sol is loaded in the sol-gel process. Such anticorrosive coatings can be applied very evenly and with homogeneous layer properties even on relatively difficult to access surface areas of the casting component, which in turn promotes overall corrosion resistance and longevity of the casting component.

In a further embodiment, the sol-gel corrosion protection layer has a zirconium-based or silicon-based gel former. In a further embodiment, the sol-gel corrosion protection layer contains an additionally added alkali metal or alkaline earth metal salt and / or an additionally added, viscosity-adjusting polymer. This contributes to the achievement of the desired good layer properties for the corrosion protection layer on corresponding melt contact surface areas of the casting component.

In a further embodiment, the sol-gel corrosion protection layer is formed as a multilayer of several coating layers, of which at least two are loaded with the microparticles and / or nanoparticles as filler and / or at least one layer layer, preferably the last layer layer, is applied without filler before then in the sol-gel process, all the gel layer layers together form a burn-in be subjected to. With such a multi-layer structure, the properties of the corrosion protection layer can be further optimized with regard to corrosion resistance to hot metal melts. Thus, for example, a filler-free outer layer layer can act as a cover layer layer of, for example, silicon oxide or zirconium oxide. The micro- and / or nanoparticles then remain embedded in the underlying layer or layers.

In a development of the invention, the casting-technical component is one for a device for casting an aluminum melt. Due to the mentioned, outstanding corrosion resistance against hot aluminum melts, the casting component according to the invention is outstandingly suitable for this purpose.

In a development of the invention, the casting component is one for a metal die casting machine. In particular, it may be a casting assembly, a casting vessel, a melt furnace component, a melt delivery component, a casting component, or a portion of these melt-contacting components of the metal die casting machine. Due to its specific corrosion protection layer, the casting component also has excellent suitability and comparatively long service life for these applications.

With the method according to the invention, a corrosion protection layer is applied to a substrate by a sol-gel process using micro- and / or nanoparticles with an average particle size between 100 nm and 50 μm as filler. In particular, the substrate may be a casting component according to the invention, on the melt-contact surface area of which the anticorrosive coating is applied. In addition, the substrate may also be any component whose surface is to be protected from corrosive attack of a reactive molten metal. In a further development of the method, a plurality of gel layer layers with micro- and / or nanoparticles of the same or different substances are formed before the layer layers are subjected together to a curing, vitrification baking step.

In a further development of the method, a plurality of gel layer layers are formed, wherein at least for a last layer layer a filler-free sol material is used. The latter forms a filler-free cover layer layer after a common, glazing baking step, while the micro- and / or nanoparticles remain embedded in the inner layer layer (s).

In a further development of the method, a vitrification baking process for the one or more gel layer layers is carried out at a temperature between about 500 ° C and about 650 ° C. It turns out that a sol-gel corrosion protection layer formed in this way has very high corrosion resistance to chemically-reactive influence of hot metal melts when using micro- and / or nanoparticles of suitable substances.

Advantageous embodiments of the invention are illustrated in the drawings and will be described below. Hereby show:

1 is a longitudinal sectional view through a casting container with corrosion protection layer for a hot chamber die-casting machine,

FIG. 2 shows a schematic sectional view of a region of the casting container provided with the anticorrosion layer and FIG 3 shows a flow chart for illustrating a method for applying a corrosion protection layer, for example for the casting container of FIG. 1.

A casting container 1 shown in Fig. 1 is of a per se conventional type, as used by the applicant in hot chamber die-casting machines, for. Cast aluminum, magnesium and zinc melts. He has a metallic body 2, which preferably consists of a steel material or stainless steel material as usual and in which various openings or holes are introduced, in particular a piston rod through hole 4, which merges at its lower end in a cylindrical melt chamber bore 5, in which at inlet bore 6, is sucked through the melt from a melt furnace or melt crucible in the melt chamber bore 5, a riser 7, is pressed through the melt from the melt chamber bore 5 to a mold, and access holes 8a, 8b, which serve to introduce the riser channel bore 7 and are closed with sealing plugs, not shown.

In use, the casting container 1 is inserted in the vertical position shown up to a marked height H in FIG. 1 into a melt crucible of the melting furnace of the die-casting machine. This has the consequence that potentially all inner and outer surfaces of the casting container 1 can come into contact with the molten metal to be poured up to this height H. In addition, this melt contact also exists for the surface of the section H of the riser channel 7 above the height H. All of these surface regions which may come into contact with the molten casting melt in the casting operation are referred to herein as melt-contact surface regions 9 and are shown in FIG thicker drawn lines highlighted. In the example shown, these are in particular the surfaces of the melt chamber bore 5 and a subsequent portion of the piston rod passage bore 4 to at least said height H, the inlet holes 3, the riser 7, the access holes 8a, 8b and the outside of the body 2 to the height H.

In these melt-contact surface areas 9, the base body 2 of the casting container 1 is provided with a characteristic, anti-molten metal corrosion protection layer 3, which is formed using micro- and / or nanoparticles of one or more selected substances. These substances are selected from a group of substances consisting of borides, nitrides and carbides of the transition metals and their alloys as well as of boron and silicon and of aluminum oxide (Al ₂ O ₃ ). The microparticles and / or nanoparticles have an average particle size of between 50 nm and 50 μm, preferably an average particle size of between 100 nm and 30 μm, and more preferably between 150 nm and 30 μm. Among other things, micro and / or nanoparticles of TiB ₂ prove to be advantageous.

The corrosion protection layer 3 is applied in an advantageous realization by a sol-gel process on the melt-contact surface regions 9 as a substrate, wherein it is said that the substrate is preferably a steel material of the casting container base body 2 as stated. In this case, the sol-gel corrosion protection layer can be realized as a single layer or multiple layer.

FIG. 2 schematically illustrates the anticorrosion layer 3 applied to the base body 2, for example made of steel or stainless steel, in this example as a multiple layer with one or more layer layers forming an outer, filler-free layer part 3b, and one or more layer layers, one from the outside Layer part 3b covered layer part 3a form, which contains the mentioned micro- and / or nanoparticles as a filler of the sol-gel process. As a result, the micro- and / or nanoparticles embedded in the inner layer part 3a of the corrosion protection layer 3, which is covered by the outer layer part as a cover layer layer 3b. Typical preferred layer thicknesses for the anticorrosive layer 3 are in the range between about 1 μΐη and 500μΐη, wherein the mean particle size of the micro- and / or nanoparticles adapted to the desired layer thickness is chosen to be smaller, so that the micro- and / or nanoparticles not protrude on the surface of the corrosion protection layer 3.

By way of example, FIG. 3 illustrates a possible advantageous method for applying a corrosion protection layer by a sol-gel process. The anticorrosive layer applied thereby may be the anticorrosion layer 3 of the casting container 1 or, alternatively, any other component used in the casting industry or otherwise having a surface which in use is to be protected from the reactive influence of a liquid molten metal. As shown, first a gel former with a solvent and secondly water are mixed with the solvent in two separate mixing steps 10, 1 1. The gelling agent used is a zirconium-based or silicon-based gelling agent, for example zirconium propoxide, tetramethoxysilane or tetramethylorthosilicate (TMOS), tetraethoxysilane or tetraethylorthosilicate (TEOS), aminopropyltrimethoxysilane (APS (M)) or aminopropyltriethoxysilane (APS (E)). As the solvent, for example, acetic acid or glacial acetic acid or tetrahydrofuran (THF) can be used. Gelling agent and solvent are typically mixed in approximately equal proportions by weight, the mixing ratio of solvent and water is 1: n mol, where n denotes the amount of gelling agent in moles multiplied by the number of ligands of the gelling agent. Subsequently, the two mixtures are mixed together, whereby it comes to an exothermic hydrolysis to form the sol as the starting material, see the mixing step 12 in Fig. 3rd

In order to provide sol loaded with filler, in a further mixing step 13, the sol is mixed with the microparticles and / or nanoparticles of one or more of the above-mentioned particulate substances, i. loaded. Preferred mean particle sizes are, as stated, in the range of 50 nm to 50 μm and in particular between 100 nm and 30 μm or 150 nm and 30 μm. The micro- and / or nanoparticles are preferably admixed in a proportion by weight which is less than or at most equal to the weight fraction of sol. After a subsequent cooling step, the loaded sol material is ready for use, the processing time typically being at most about 1 h. During this time, the component to be coated, like the casting container shown in the melt-contact surface region 3, is coated with a layer of loaded sol material, see step 15 in FIG. 3. The applied layer layer is then gel-formed at a suitable temperature of up to dried about 100 ° C, see step 16.

The steps 15 and 16 for applying a layer of prepared sol material and conversion to a gel layer layer can be repeated once or several times as needed to prepare the sol-gel layer as a multilayer, with loaded with micro- and / or nanoparticles as needed Sol material or filler-free sol material without these micro- and / or nanoparticles can be used for a respective layer position.

Thus, as an exemplary example, FIG. 3 shows the production of a last, outer layer layer of unloaded, filler-free sol material, as obtained in the mixing step 12. By a corresponding Sequence of coating step 17 and drying step 18, the unloaded sol is applied and dried to gel formation at up to 100 ° C.

It is understood that, in alternative embodiments, any desired combinations of layer layers with unloaded, filler-free sol material and layer layers with loaded sol material can be realized, wherein in the loaded sol material the mentioned micro- and / or nanoparticles of the indicated substance group are contained as filler. Furthermore, it is understood that micro-and / or nanoparticles of exclusively the same substance or alternatively different substances can be contained as needed in the same loaded layer layer and that also in different loaded layer layers as needed micro- and / or nanoparticles of the same substance or may be contained in different substances. Among others, micro and / or nanoparticles of TiB ₂ , M0 ₂ B ₅ , ZrB ₂ and mixtures of these substances have proven to be particularly suitable.

After a desired single-layer or multi-layer layer structure of one or more gel layer layers has been produced in this way, this layer structure is cured in a final stoving step 19 of the sol-gel process and thus compacted to a glassy material. The baking step 19 is preferably carried out at a temperature between 500 ° C and 650 ° C. Preferably, a protective atmosphere is e.g. from argon gas used for the baking process.

If an unloaded silicon-based gelling agent is used to apply the last layer layer according to steps 17 and 18 of FIG. 3, the filler-free cover layer 3b according to FIG. 2, for example as a silicon oxide layer, can be realized therefrom. It is understood that the invention includes other embodiments besides the exemplary embodiments shown and explained above. If necessary, the casting container 1 can also be provided with the anticorrosion layer or another surface layer on further surface regions which are not subject to melt contact. In addition, any other casting components may be provided with the anticorrosive layer, at least in their melt contact surface area, in particular cast sets, melt furnace components, melt delivery components and mold components or parts thereof of hot chamber or cold chamber die casting machines and other devices for casting a molten metal. In the same way, any other components can be provided by the method according to the invention with a corrosion protection layer in surface areas, which can come in contact with molten metal in use, for example, components or equipment, such as for handling molten metal in soldering processes, in the manufacture of metal alloys, in cleaning of molten metals and in the recovery of solid metals from the melt.

It turns out that the special corrosion protection layer has a very high corrosion resistance, in particular also with respect to hot aluminum melts. When the corrosion protection layer is formed by means of a sol-gel process, the layer can be applied very evenly and homogeneously even in hard to reach surface areas of the casting component to be coated with relatively little effort. If necessary, an alkali or alkaline earth metal salt and / or a viscosity-adjusting polymer may additionally be added to the sol material for the sol-gel layer. In alternative embodiments of the invention, the corrosion protection layer can also be applied by laser cladding, flame spraying or plasma spraying. Further embodiments of the invention include the application of a multilayer anticorrosion layer, of which at least one, preferably an outer, layer layer is formed by the sol-gel coating method according to the invention and at least one other layer layer by another application method, which is in particular laser cladding, flame spraying or plasma spraying can act. In this way, in appropriate applications, a layer structure adapted optimally to the intended use can be achieved with minimized production outlay. In the same way, any component or substrate can be provided according to the invention at different surface areas, each with a corrosion protection layer, which are applied with two different of the four mentioned application methods, ie sol-gel method, laser cladding, flame spraying and plasma spraying. For example, the sol-gel process can be used to coat hard-to-reach areas and one of the other three methods mentioned can be used to coat more accessible, flat areas of the substrate. Furthermore, the mentioned variants of the "vertical" or "lateral" combination of layers applied with different methods can also be combined with one another in a corresponding component or substrate.

Claims

claims

1. casting component for a device for casting or handling a molten metal, wherein the component has a metallic base body (2) and a melt contact surface area (9), which is exposed in the casting operation of the molten metal,

characterized in that

the metallic base body (2) is provided in the melt-contact surface area (9) with a corrosion-resistant layer (3) which is resistant to the molten metal and which is formed by using micro- and / or nanoparticles of one or more substances from a group of substances consisting of bonding , Nitrides and carbides of the transition metals and their alloys, as well as of boron and silicon and of Al 2 O 3.

2. casting component according to claim 1, further characterized in that the micro- and / or nanoparticles have an average particle size between 50nm and 50μΐη, in particular between 100nm and 30μΐη.

3. Casting component according to claim 1 or 2, further characterized in that the corrosion protection layer is formed using micro and / or nanoparticles of TiB ₂ .

4. Casting component according to one of claims 1 to 3, further characterized in that the corrosion protection layer is a sol-gel layer with the micro- and / or nanoparticles as a filler.

5. casting component according to claim 4, further characterized in that the sol-gel layer comprises a zirconium-based or silicon-based gelling agent.

6. casting component according to claim 4 or 5, further characterized in that the sol-gel layer comprises an additionally added alkali or alkaline earth metal salt and / or additionally added, viscosity-adjusting polymer.

7. casting component according to claim 5 or 6, further characterized in that the sol-gel layer is formed by a plurality of gel layer layers, of which at least two micro and / or nanoparticles of the same or different substances and / or at least one layer layer is formed without micro- and / or nanoparticles.

8. Casting component according to one of claims 1 to 7, further characterized in that the base body is formed of a steel material.

9. Casting component according to one of claims 1 to 8, further characterized in that the casting component is one for a device for casting an aluminum melt.

10. casting component according to one of claims 1 to 9, further characterized in that the casting component is such for a metal die casting machine, in particular a Gießgarnitur, a casting container, a Schmelzeofenkomponente, a Schmelzeförderkomponente, a casting component or a part of one of these die casting machine components.

1 1. A method for applying a corrosion protection layer on a substrate, in particular a casting component according to one of claims 1 to 10, by a sol-gel process using micro and / or nanoparticles having an average particle size between 100nm and 30μΐη as a filler ,

12. The method of claim 1 1, further characterized in that in the sol-gel process, a plurality of gel layer layers are formed, of which at least two loaded with the micro and / or nanoparticles of the same or different substances as a filler.

13. The method of claim 1 1 or 12, further characterized in that in the sol-gel process, a plurality of gel layer layers are formed, of which at least one last filler-free without the micro- and / or nanoparticles is applied.

14. The method according to any one of claims 1 1 to 13, further characterized in that after forming one or more gel layer layers, a vitrifying baking step at a temperature between 500 ° C and 650 ° C is performed.