EP2723916A2 - Élément fabriqué par une technique de coulée et procédé d'application d'une couche de protection contre la corrosion - Google Patents

Élément fabriqué par une technique de coulée et procédé d'application d'une couche de protection contre la corrosion

Info

Publication number
EP2723916A2
EP2723916A2 EP12729600.2A EP12729600A EP2723916A2 EP 2723916 A2 EP2723916 A2 EP 2723916A2 EP 12729600 A EP12729600 A EP 12729600A EP 2723916 A2 EP2723916 A2 EP 2723916A2
Authority
EP
European Patent Office
Prior art keywords
casting
layer
nanoparticles
micro
sol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12729600.2A
Other languages
German (de)
English (en)
Other versions
EP2723916B1 (fr
Inventor
Norbert Erhard
Helmar Dannenmann
Jürgen KURZ
Andreas Sydlo
Daniel Gerner
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.)
Oskar Frech GmbH and Co KG
Original Assignee
Oskar Frech GmbH and Co KG
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 Oskar Frech GmbH and Co KG filed Critical Oskar Frech GmbH and Co KG
Priority to PL12729600T priority Critical patent/PL2723916T3/pl
Publication of EP2723916A2 publication Critical patent/EP2723916A2/fr
Application granted granted Critical
Publication of EP2723916B1 publication Critical patent/EP2723916B1/fr
Active 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
    • B22D17/2015—Means for forcing the molten metal into the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/08—Features with respect to supply of molten metal, e.g. ingates, circular gates, skim gates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D15/00—Handling or treating discharged material; Supports or receiving chambers therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof

Definitions

  • 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 G cardgarnituren, casting containers, melting furnaces, melt delivery units and molds and parts of these Metallg discernkomponenten.
  • a steel material is used for the base body, since such components have a good cost / benefit ratio.
  • 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.
  • 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.
  • 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.
  • 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.
  • the presence of the one or more anti-corrosive substances in the form of micro- and / or nanoparticles in the layer is primarily assumed.
  • 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.
  • the micro- and / or nanoparticles have an average particle size between 50 nm and 50 ⁇ m.
  • average particle sizes between 100 nm and 30 ⁇ m, and more particularly between 150 nm and 30 ⁇ m, prove to be very advantageous for the corrosion protection layer designed for resistance to hot, reactive molten metals.
  • the corrosion protection layer contains at least microparticles and / or nanoparticles of TiB 2 .
  • 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.
  • 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.
  • 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.
  • the sol-gel corrosion protection layer has a zirconium-based or silicon-based gel former.
  • 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.
  • 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.
  • the properties of the corrosion protection layer can be further optimized with regard to corrosion resistance to hot metal melts.
  • 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.
  • 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.
  • the casting component is one for a metal die casting machine.
  • 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.
  • 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 ⁇ m as filler.
  • the substrate may be a casting component according to the invention, on the melt-contact surface area of which the anticorrosive coating is applied.
  • the substrate may also be any component whose surface is to be protected from corrosive attack of a reactive molten metal.
  • 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.
  • 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).
  • 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.
  • 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
  • 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.
  • 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
  • melt-contact surface regions 9 are shown in FIG thicker drawn lines highlighted.
  • 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.
  • 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 ⁇ m, preferably an average particle size of between 100 nm and 30 ⁇ m, and more preferably between 150 nm and 30 ⁇ m.
  • 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.
  • 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.
  • 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 ⁇ and 500 ⁇ , 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.
  • 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.
  • 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)).
  • TMOS tetramethoxysilane or tetramethylorthosilicate
  • TEOS tetraethoxysilane or tetraethylorthosilicate
  • APS (M) aminopropyltrimethoxysilane
  • APS (E) aminopropyltriethoxysilane
  • THF acetic acid or glacial acetic acid or tetrahydrofuran
  • 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
  • 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 ⁇ m and in particular between 100 nm and 30 ⁇ m or 150 nm and 30 ⁇ m.
  • 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.
  • the loaded sol material is ready for use, the processing time typically being at most about 1 h.
  • 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.
  • FIG. 3 shows the production of a last, outer layer layer of unloaded, filler-free sol material, as obtained in the mixing step 12.
  • the unloaded sol is applied and dried to gel formation at up to 100 ° C.
  • 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.
  • 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.
  • micro and / or nanoparticles of TiB 2 , M0 2 B 5 , ZrB 2 and mixtures of these substances have proven to be particularly suitable.
  • 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.
  • a protective atmosphere is e.g. from argon gas used for the baking process.
  • the filler-free cover layer 3b according to FIG. 2 for example as a silicon oxide layer, can be realized therefrom.
  • the invention includes other embodiments besides the exemplary embodiments shown and explained above.
  • 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.
  • 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.
  • 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.
  • the special corrosion protection layer has a very high corrosion resistance, in particular also with respect to hot aluminum melts.
  • 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.
  • 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.
  • the corrosion protection layer can also be applied by laser cladding, flame spraying or plasma spraying.
  • a layer structure adapted optimally to the intended use can be achieved with minimized production outlay.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Nanotechnology (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Coating With Molten Metal (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne un élément fabriqué par une technique de coulée et un procédé d'application d'une couche de protection contre la corrosion. L'invention concerne un élément fabriqué par une technique de coulée pour un dispositif de coulée d'une masse fondue métallique. L'élément comporte un corps de base métallique (2) et une zone de surface en contact avec la masse fondue (9) exposée au cours de l'opération de coulée à la masse fondue métallique. L'invention concerne également un procédé d'application d'une couche de protection contre la corrosion sur un substrat, celui-ci étant en particulier un élément fabriqué par une technique de coulée. Pour l'élément selon l'invention fabriqué par une technique de coulée, le corps de base métallique est pourvu dans la zone de surface en contact avec la masse fondue d'une couche de protection contre la corrosion (3) résistante à la masse fondue métallique et formée au moyen de microparticules et/ou de nanoparticules d'une ou de plusieurs substances choisies dans un groupe de substances constitué par les borures, les nitrures et les carbures des métaux transitoires et leurs alliages et constitué de bore et de silicium et de Al2O3. Il peut être utilisé par exemple pour des contenants coulés et d'autres éléments de machines de coulée sous pression d'aluminium.
EP12729600.2A 2011-06-24 2012-06-22 Élément fabriqué pour la technique de coulée et procédé d'application d'une couche de protection contre la corrosion Active EP2723916B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL12729600T PL2723916T3 (pl) 2011-06-24 2012-06-22 Element konstrukcyjny techniki odlewniczej i sposób nakładania warstwy antykorozyjnej

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011078066A DE102011078066A1 (de) 2011-06-24 2011-06-24 Gießtechnisches Bauteil und Verfahren zum Aufbringen einer Korrosionsschutzschicht
PCT/EP2012/062082 WO2012175668A2 (fr) 2011-06-24 2012-06-22 Élément fabriqué par une technique de coulée et procédé d'application d'une couche de protection contre la corrosion

Publications (2)

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EP2723916A2 true EP2723916A2 (fr) 2014-04-30
EP2723916B1 EP2723916B1 (fr) 2019-01-16

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EP12729600.2A Active EP2723916B1 (fr) 2011-06-24 2012-06-22 Élément fabriqué pour la technique de coulée et procédé d'application d'une couche de protection contre la corrosion

Country Status (13)

Country Link
US (1) US10766064B2 (fr)
EP (1) EP2723916B1 (fr)
JP (1) JP6073305B2 (fr)
KR (1) KR102019176B1 (fr)
CN (1) CN103930597B (fr)
BR (1) BR112013032678B1 (fr)
DE (1) DE102011078066A1 (fr)
ES (1) ES2719125T3 (fr)
MX (1) MX372828B (fr)
PL (1) PL2723916T3 (fr)
RU (1) RU2578301C2 (fr)
TR (1) TR201905070T4 (fr)
WO (1) WO2012175668A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3027033B1 (fr) * 2014-10-10 2019-05-03 Rbnano Procede de revetement de la surface d'un substrat metallique
GR1009951B (el) * 2019-07-26 2021-03-09 Oskar Frech Gmbh & Co. Kg Εξαρτημα χυτευσης και μεθοδος για εφαρμογη αντιδιαβρωτικου στρωματος
DE102020210913A1 (de) * 2020-08-28 2022-03-03 Oskar Frech Gmbh + Co. Kg Gießtechnisches Bauteil mit Korrosionsschutzschichtaufbau
CN117753928B (zh) * 2024-02-22 2024-04-26 潍坊卓安重工科技有限公司 利用球墨铸铁制造球磨机端盖的消失模铸造方法

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Also Published As

Publication number Publication date
TR201905070T4 (tr) 2019-05-21
JP6073305B2 (ja) 2017-02-01
KR20140043112A (ko) 2014-04-08
EP2723916B1 (fr) 2019-01-16
US20140193635A1 (en) 2014-07-10
MX372828B (es) 2020-07-03
US10766064B2 (en) 2020-09-08
BR112013032678B1 (pt) 2020-11-10
WO2012175668A2 (fr) 2012-12-27
CN103930597B (zh) 2016-09-14
WO2012175668A3 (fr) 2014-04-03
RU2578301C2 (ru) 2016-03-27
MX2013014924A (es) 2014-05-09
BR112013032678A2 (pt) 2017-01-24
RU2014101456A (ru) 2015-07-27
ES2719125T3 (es) 2019-07-08
CN103930597A (zh) 2014-07-16
DE102011078066A1 (de) 2012-12-27
KR102019176B1 (ko) 2019-09-09
PL2723916T3 (pl) 2019-07-31
JP2014519985A (ja) 2014-08-21

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