EP2370211B1 - Components for high temperature applications - Google Patents
Components for high temperature applications Download PDFInfo
- Publication number
- EP2370211B1 EP2370211B1 EP09764801.8A EP09764801A EP2370211B1 EP 2370211 B1 EP2370211 B1 EP 2370211B1 EP 09764801 A EP09764801 A EP 09764801A EP 2370211 B1 EP2370211 B1 EP 2370211B1
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- European Patent Office
- Prior art keywords
- rail
- layer
- coating
- silicon
- pull
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- 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
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- 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
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- 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
- C23C18/1233—Organic substrates
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- 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
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- 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
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- 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
- C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
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- 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
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- 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
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
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- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Definitions
- the invention relates to a component according to the preamble of claim 1.
- the DE 10 2007 010 955 A1 discloses a silane-based coating on a furnace steel part and applied to the steel surface in a sol-gel process. This coating has a layer thickness of 1-6 mm.
- the DE 25 44 880 discloses a method of making an abrasion resistant coating on plastic or metal substrates made from a coating composition from a titanium, aluminum or zirconium ester with at least two ester groups OR, an epoxy and / or acryloxysilane and optionally conventional additives and fillers.
- the EP 0 973 958 discloses a method of providing a metallic surface with a vitreous layer wherein a coating composition is applied to a metallic surface and thereafter thermally densified to a transparent vitreous layer at a temperature of at least 350 ° C.
- the DE 10 2004 001 097 discloses a metallic substrate having a deformable vitreous coating comprising a coating sol applied by applying an alkali silicate-containing coating sol to the substrate followed by a two step thermal treatment.
- the first stage can be carried out in an oxygen-containing atmosphere or in vacuo at a residual pressure of ⁇ 15 mbar.
- the second stage is carried out in an oxygen-deficient atmosphere until complete densification and curing of the vitreous layer. In this process, the generation and guarantee of the different atmospheres in the thermal compression is associated with additional effort in this process.
- the EP 1 137 729 discloses a coating for household appliances which is based on hydrolyzable silanes and has at least one nonhydrolyzable component.
- the hydrolyzable silanes have epoxide groups at least one non-hydrolyzable substituent, and a curing catalyst selected from the group of Lewis bases zirconium titanium or aluminum alkoxides and also nanoscale inorganic solids.
- the DE 10 2007 053 023 discloses a laminating composition with an oxide compound and a method of coating substrates, including metal.
- a coating composition is applied to the substrate applied, which represents the general formula, for example, a silane.
- this silane composition is heated to a temperature of more than 400 ° C. to form an element / element oxide composite layer, and subsequently this element oxide composite structure is heated and solidified by local sintering by means of a laser, which means additional expenditure on equipment compared to previous heating methods.
- the EP 0 928 457 discloses a method for producing substrates having high temperature and UV resistant transparent colored coatings, wherein the coating composition can form at least one glassy crystalline or partially crystalline oxide and contains at least one member of the group of a metal compound and the coating thermally cures to form a coated substrate ,
- the EP 0 729 442 discloses a process for producing a functional vitreous layer comprising at least one hydrolyzable silane, at least one organosilane and at least one functional carrier for coloring the coating or for coloring or improving the metallic appearance. Subsequently, this coating is thermally compressed to a glassy layer.
- the EP 1 068 372 A1 describes a method of protecting a metallic substrate from corrosion.
- a metal-derived species X is formed.
- the substrate is provided with a coating of polysiloxanes, wherein the coating also comprises a species Z, which forms a species Y with the metal.
- the formation of the species Y has a lower formation enthalpy than the formation of the species X.
- the formation of the species Y is preferred.
- the thermal cycling stability was confirmed over a range of -40 ° C-100 ° C. A thermal cycling over a range of - 40 ° C to 500 ° C under the corrosive conditions, such as occur in the furnace, are not disclosed in the document.
- the DE 10351467 discloses a substrate having a double coating.
- This coating can be used, for example, in the oven interior come.
- the double coating has a hydrophobic component which reacts with free OH groups as the outer layer.
- the inner layer is an inorganic sol-gel layer in which the outer hydrophobic layer is only applied at moderate temperatures of up to 100 ° C and is firmly anchored by condensation reactions with this chemically.
- the baking of the double layer system takes place on the surface of the article.
- the DE 10155613 discloses a process for coating surfaces by hybrid polymeric materials and the coating solutions or compositions used therein. This is a layer of silanes with org. Rests and aluminum alkoxides applied to the surface of the substrate and dried. Subsequently, the surface is provided with a topcoat.
- the DE 10253839 A1 discloses a method of coating articles with metallic surfaces.
- at least one organosilane is applied in the so-called sol-gel process and the resulting coating is converted into a polysiloxane coating.
- This conversion of the coating into a polysiloxane coating is preferably carried out by thermal treatment at temperatures of 100 ° C.
- the EP 0956373 discloses a method of providing a protective surface on a base alloy containing iron, nickel and chromium.
- elemental silicon and titanium with at least aluminum or chromium are deposited on the base alloy and heat treated to form a surface alloy.
- Coated fittings and components with applications in the high temperature range are in the DE 102005039883 disclosed. It describes an appliance accessory for the oven, the appliance accessory has a base made of metal, such as chromed steel and a pyrolysis resistant coating. The coating material is glassy and was applied to the base body from a liquid phase.
- the object of the present invention is therefore to provide a method which improves the resistance of components to environmental influences, in particular when used in the high-temperature range.
- the present invention solves this problem by a component having the features of claim 1.
- the method for manufacturing components provides for providing a blank, preferably by punching and bending a metal sheet, and applying an inorganic-organic hybrid polymer layer on the surface of the blank, heating the coated blank, for example to a temperature of at least 400 ° C and the cooling of the coated blank to room temperature.
- the blank may preferably be made of metal, for example of stainless steel, steel, aluminum, aluminum alloys, copper, copper alloys, zinc, chromium or nickel.
- the inorganic-organic hybrid polymer layer can also be applied to blanks which are already coated with PTFE (polytetrafluoroethylene) or PEEK (polyetheretherketone).
- PTFE polytetrafluoroethylene
- PEEK polyetheretherketone
- LCP liquid crystal polymer
- thermoplastics, ceramics and enamel the hybrid polymer layer can be applied.
- various methods of shaping are applicable during the manufacturing process of the blank, depending on its material properties.
- the inorganic-organic Hybrid polymer coating and subsequent thermal treatment provides improved corrosion protection even in the higher temperature range compared to the previous passivation.
- the resulting polymer forms a hard layer, which is also more tear-resistant than would be the case, for example, when applying a purely inorganic material.
- This additional strength of the coating as a result of the thermal treatment therefore makes it more resistant to mechanical abrasion and ensures the maintenance-free use of the components produced by this method.
- the particularly material-saving and simple application method of spraying the sol onto the surface of the blank can be used.
- fluorine-containing silanes as a starting material for the sol-gel process, the surfaces oleophobic and hydrophobic properties can be obtained, they are thus dirt-repellent.
- An advantageous curing of the coating provides UV irradiation, so that as a result of three-dimensional crosslinking of the polymer layer, the surface becomes scratch-resistant and more resistant to abrasion. Therefore, the blank can be stored for a long time after this step before it is further processed.
- the treated components can, for example, even at low temperatures after this treatment step used in refrigerators, freezers and ovens at service temperatures between -50-600 ° C.
- when used in refrigerators and freezers can thus be dispensed with the expensive higher or even additional zinc coating on the components.
- sol further inorganic components such as SiO 2 and / or TiO 2
- the sol further inorganic components add in order to achieve by incorporation of these components in the inorganic-organic hybrid polymer structure during polymerization, an additional improvement of the mechanical properties of the coating.
- additives may be aluminum and / or manganese compounds. These compounds can be incorporated into the inorganic-organic hybrid polymer structure during hydrolysis. After a thermal treatment of the component at up to 800 ° C, aluminum and / or manganese can be incorporated into the predominantly inorganic network of the coating.
- An advantageous embodiment of the coating provides a silicon-aluminum and / or titanium-containing inorganic-organic hybrid polymer, which at temperatures up to 800 ° C, preferably in the range of 400-600 ° C, is stable.
- Aluminum, titanium and silicon oxygen polymer compounds are inexpensive, easy to synthesize and chemically resistant to most chemicals. Due to their material properties, such polymers find many applications as building materials or even coating material and thus meet the requirements that are placed on coating material for high temperature application.
- the heat treatment of the inorganic-organic hybrid polymer coating is advantageously carried out according to a temperature program, two different temperature gradients being used in a heating phase of the coated green body.
- a significantly faster heating phase in order to achieve the corresponding target temperature ⁇ 2 .
- the coating is allowed at Adjust the thermal expansion of the blank to the changed conditions and, if necessary, to reorient along the substrate surface.
- the controlled heating is therefore advantageous in that hardened coatings tend to crack in the higher temperature range.
- the inorganic-organic hybrid polymer coated blank is preferably annealed for at least 20 minutes, more preferably for more than 30 minutes, at least 200 ° C, preferably 300-600 ° C.
- an adherent, corrosion-resistant and largely age-resistant substrate-polymer compound is achieved.
- this temperature range for example, the pyrolysis of a furnace.
- the time of at least 20 or 30 minutes is advantageous, since at this high temperature, an oxidation of the organic hybrid polymer components takes place, and thus after the oxidation of the organic components a finely divided and more tear-resistant polymer layer is formed, than when using only inorganic starting materials.
- the coated blank is annealed at an air flow rate of 30-90 l / min, preferably 50-70 l / min, whereby as complete as possible oxidation of the organic moieties of the hybrid polymer is achieved on the substrate surface and subsequent exposure of the user by Combustion products of any post-combustion of organic polymer components is excluded.
- the component is smoothed before applying the inorganic-organic hybrid polymer layer in order to achieve the largest possible interface between the forming polymer surface and the substrate surface and also to obtain a small distance between both surfaces.
- the component may have a surface roughness of at most 500 nm, for example from 300 to 500 nm, preferably before coating 300 to 400 nm, which improves the adhesion of the polymer to the substrate surface.
- cleaning methods such as degreasing may be used prior to application of the inorganic-organic hybrid polymer layer.
- a component produced by the method according to the invention can be used in particular in ovens in the high temperature range, because the coating causes both a high material load capacity and a high temperature resistance.
- food is usually cooked, which usually contains a lot of water, which evaporates and precipitates elsewhere. This is a special susceptibility to corrosion in components in an oven.
- especially in this application area should be placed on a hygienic quality processing value.
- a component coated by the method according to the invention can be used as a fitting in other domestic appliances in the range between -50 ° C. to 600 ° C. This includes u.a. also the use in refrigerators, where particularly high demands on the corrosion resistance of fittings, for example by salt spray tests and the like., Are provided.
- the component can be used in particular as a fitting, such as be designed as a hinge, as flap fitting, as a rail system, as a food support and as a pull-out guide, or as part of a fitting.
- the inorganic-organic hybrid polymer coating also increases the corrosion resistance during transport of the components, in particular the resistance to external climatic influences such as rain, snow, salt water, seawater spray and fog increases.
- external climatic influences such as rain, snow, salt water, seawater spray and fog increases.
- containers are protected against external influences, condensate can nevertheless form inside.
- the current temperature and the moisture that is brought into the container during loading affect the current relative humidity in the container.
- the trapped air in the container, the cargo, its packaging or the dunnage are sources of moisture.
- a coating is provided which is resistant to corrosion, in particular during sea transport of the coated components elevated.
- a use of the coated components in seawater climate is possible.
- the components can be used in the form of furniture fittings in kitchen and / or laboratory furniture used for the storage of cleaning agents or chemicals.
- dyes and / or pigments can be incorporated into the coating of the component. This is advantageous for achieving optical effects since possible tarnish colors of stainless steels are laminated in color or by metallic optics.
- these precoated components may already be colored
- the component according to the invention is particularly well suited for the production of a pullout guide, in particular, the rails of the pullout guide can be coated accordingly.
- Fig. 1 shows a pullout guide for high temperature applications, in particular for ovens, comprising a guide rail 1 and a guide rail 2 movable relative to the guide rail, between which a middle rail 3 (see Fig. 2 ) is stored.
- pullout guides are known, which have only a guide and a running rail.
- pull-out guides are also used which have a guide rail, a running rail and more than one middle rail.
- rolling elements 4 in particular made of ceramic, are provided for the movable mounting of the middle rail 3 and the running rail 2 .
- rolling elements 4 in particular made of ceramic, are provided for the movable mounting of the middle rail 3 and the running rail 2 .
- a plurality of raceways 6 are provided for the spherical rolling elements 4 on the guide rail 1, the middle rail 3 and the running rail 2.
- the rolling elements 4 are spaced from each other in the rolling element cage 5 to not touch each other during rolling, whereby the smooth running would be hindered.
- the rails 1 to 3 are made for use in ovens from a stamped and bent sheet steel and provided with a coating.
- the production of the components of the pullout guide, in particular the rails 1 to 3 takes place by the following steps:
- the metallic blanks of the pullout guide are made by punching and bending.
- the blank can be machined.
- an inorganic-organic hybrid polymer layer is applied on the surface of the blanks.
- the coated blanks are then heated to a temperature of at least 400 ° C and annealed for a predetermined period of time before being recooled to room temperature.
- the application of the inorganic-organic hybrid polymer layer takes place in the sol-gel process, which in Fig. 3 is exemplified for a polysiloxane coating.
- alkoxy compounds of silicon are converted by hydrolysis, with substitution of the alkoxy functions, by hydroxy groups into reactive silanols present in the sol as colloidal particles. These particles are deposited on the application of the sol on a surface, preferably of metal, at this. Heating further enhances the interaction of silanol molecules with the surface, leading to the formation of covalent bonds. When heated, it also leads to the transformation of the sol in the gel state to form polysiloxanes. In this case, alcohols and water are formed in a condensation reaction.
- the coating sols of the inorganic-organic hybrid polymers can be applied in liquid form to a metallic component in a sol-gel process and flow and harden under mild reaction conditions.
- silicon As the inorganic component, it is also possible, for example, to use metals such as zirconium or titanium alkoxy compounds.
- TMOS tetramethoxysilane
- solvent about 1/4 of the volume of the TMOS
- slow addition about 2 h
- the addition is in the range between 0-10 ° C, since TMOS is very flammable, toxic and corrosive.
- TMOS is very flammable, toxic and corrosive.
- HCl concentrated aqueous HCl
- the HCl can be cooled down to a temperature of about 0 ° C in advance.
- the stirring is maintained for a few minutes, for example, 5-10 minutes.
- the solvent may be protic or aprotic polar, for example isopropanol.
- a mixture of mainly 3-glycidyloxypropyltrimethoxysilane (GPTS) and titanium tetraisopropylate may be converted into a flowable coating substance under basic or acidic conditions by hydrolysis and then converted into an inorganic silicon dioxide layer by subsequent curing as a result of condensation at 700-800 ° C.
- GPTS 3-glycidyloxypropyltrimethoxysilane
- titanium tetraisopropylate may be converted into a flowable coating substance under basic or acidic conditions by hydrolysis and then converted into an inorganic silicon dioxide layer by subsequent curing as a result of condensation at 700-800 ° C.
- an intermediate layer is formed between the upper silicon dioxide layer, with a thickness of 0.1-2 ⁇ m and the surface of the metallic component, which in addition to the silicon dioxide also forms an increased proportion of metal compounds or elemental metals such as chromium, aluminum and / or manganese.
- the metallic component may optionally have a chromium- or aluminum-containing alloy in which predominantly aluminum atoms diffuse into the silicon layer to form an intermediate layer.
- the diffusion of chromium, manganese, aluminum but also nickel compounds in the silicon-containing layer is surprisingly greater than the diffusion of iron compounds in this layer.
- the diffusion of the metal compounds by a temperature gradient during curing can advantageously be influenced with regard to the penetration depth and concentration distribution in the layer.
- the metal for example aluminum
- the metal may already be incorporated as part of the inorganic-organic hybrid polymer layer and accumulate in the center of the coating as a result of diffusion and distribution effects.
- Manganese may diffuse from the metal into the inorganic-organic hybrid polymer layer during heating and accumulate in this layer.
- a passivating intermediate layer can form, which, like the vitreous silicon cover layer, is temperature-resistant even at over 500.degree.
- the integrity of the layer is also retained if the component coated in this way is exposed to a welding flame of 1000-1500 ° C. for a short time, ie for about 30 minutes.
- the coating can be at least partially applied and used on metallic components, which are welded to an uncoated surface with another metallic surface. In this case, if the welding flame comes into contact with a coated area of the fitting, the coating is not destroyed.
- the coating can also be applied to a chromed surface by the sol-gel method, wherein the chromium-silicon oxide coating does not flake off at higher load in a subsequent bending of the component, compared to a pure chromated surface.
- the application of the liquid sol to the surface of the metallic component can be done by spraying, dipping, brushing or the like.
- the organic constituents of the inorganic-organic hybrid polymer can additionally crosslink three-dimensionally, which gives the coating advantageous mechanical properties.
- inorganic components for example, titanium oxide or silicon oxide may be incorporated by encapsulation in a polysiloxane coating, whereby the mechanical properties of the coating can also be improved.
- the further inorganic components can be incorporated as fine particles, in particular in the nanoscale range between 40 nm and 500 nm.
- the inorganic-organic hybrid polymer layer is heated in temperature gradients to a temperature in the range of 400-600 ° C, whereby the organic moieties of the polymer are preferentially oxidized.
- the inorganic-organic hybrid polymer in conjunction with the sol-gel process provides a network density which has low layer thicknesses, preferably between 1.0-5.0 ⁇ m, for example one on silicon based polymer layer and the incorporation of other nanoscale inorganic components as well as dyes or pigments in the polymer layer allow.
- the annealing time is between 40 minutes and 3 hours, preferably 1 hour at 200-800 ° C, preferably 300-600 ° C.
- This polymer layer is quartz-like, tear-resistant, mechanically resilient and protects the blank from corrosion. In addition, it conceals temper colors of steel-containing materials, for example as a metallic finish.
- the surfaces 1.4016 and 1.4301 are metallic surfaces of pullout guides.
- the PEEK-coated pullout guide of the experimental procedure 3 can not be loaded at 500 ° C. for 2 h, but has an improved non-sticking effect and cleaning compared with Examples 1 and 2.
- a sol-gel coating in conjunction with a PEEK coating on a pullout guide advantageously allows the high-temperature use as well as an improvement in the cleanability and thus the full Pyrolysetaugrete.
- FIG. 3 schematically a temperature diagram for the process of permanent coating of fittings, side rails and food supports for high temperature applications is shown.
- the cleaning of the metallic or plastic surface of the blank prior to the application of the inorganic-organic hybrid polymer coating can be carried out by various mechanical and / or chemical cleaning methods. Furthermore, an additional surface treatment for roughening the surface can take place.
- the flow behavior can be adjusted so that it adheres even to vertical surfaces.
- the component according to the invention with the corresponding inorganic-organic hybrid polymer coating, has the advantages of scratch resistance, abrasion resistance, corrosion protection, improved cleanability, and reduction of dirt adhesion. It is, unlike metallic coatings, transparent and can be applied to a colored substrate.
- Fig. 4 shows in tabular form the elemental composition in mass concentrations along a depth profile of a component coated according to the invention.
- Fig. 5 is shown the graphical representation of measured values of the elementary composition of the coated component over a depth profile of 0-65 microns.
- the step size of the measuring points is 0.5 ⁇ m in the range of 0-20 ⁇ m and 4 ⁇ m in the range of 20-65 ⁇ m.
- the elemental composition at 65 ⁇ m corresponds essentially to the composition of the chromium steel of the metallic component before the coating.
- the measured data in the FIGS. 4 and 5 were determined by optical glow discharge spectroscopy (sputtering gas Ar 5.0, anode diameter 2.5 mm).
- the examined component itself is a profile piece of an oven extractor guide coated according to the method of the invention.
- the component was thermally treated with 500 pyrolysis cycles at 500 ° C for 1.5 hours prior to the test.
- the table of Fig. 4 shows exemplarily selected individual values of the spectroscopic determination by means of glow discharge.
- the layer consists predominantly of oxygen-containing compounds.
- predominantly silica with a mass fraction of about 19% is represented.
- the proportion of oxidic silicon compounds is about 1.6 times higher than the proportion of metallic oxides. Iron is contained in this area of the layer with a mass fraction of 2.6%.
- the percentage by weight of oxygen-containing compounds, compared to the composition at a layer thickness of 1 micron, has decreased by about 10%.
- the mass fraction of silicon compounds is 24%.
- the mass fraction of silicon compounds is still 1.2 times higher than the mass fraction of the metallic compounds. In this case, the metal composition has changed compared to the composition of the layer at 1 micron.
- the mass fraction w (aluminum) of the layer is 12.1% and the manganese content is 11.1%.
- the silicon mass fraction is 20.9%.
- the oxygen mass fraction is 33.3%. It is noteworthy that the iron content compared to the aluminum and manganese content occupies only 6.6%.
- the iron mass fraction is already 14.6% and grows in the further profile profile up to about 70%.
- transition of the aluminum, manganese and silicon-rich and low-iron layer in an iron / chromium layer takes place at about 20 microns.
- composition at 100 ⁇ m essentially reflects the elemental composition of the chromium steel used.
- Fig. 5 shows an increase in the concentration of aluminum to 40% and manganese to 8% in the coating, the concentrations reach their maximum in the range between 10-20 microns and then drops again.
- a diffusion and distribution of aluminum and manganese compounds in the silicon-containing layer was carried out after application of the inorganic-organic silicon-containing hybrid polymer layer in the sol-gel Method and heating the coating to 550-800 ° C, preferably 650-750 ° C.
- the two-layer coating thus obtained gives rise to a variety of possible applications.
- the surface can be designed according to the customer's wishes.
- a leveling of the surface by applying the coating leads to a better cleanability of the surface and to an attractive appearance.
- Fig. 6 shows a light microscopic reproduction of the layered structure of the coated component at a scale of 50 microns.
- the intermediate layer 102 which in addition to silicon compounds mainly comprises manganese and aluminum compounds.
- the layer has an inhomogeneous structure, which is evidenced by a large number of darker and lighter points in the gray layer.
- these concentration focuses are smaller and more evenly distributed in the layer than is the case with the underlying steel layer 103.
- the layer thickness is 20-30 ⁇ m.
- the measured values are the averaged values of a triple measurement, the measured values being subject to an average fluctuation range of 5%, based on the averaged value.
- the measurement was carried out by means of energy-dispersive X-ray emission spectroscopy (EDX).
- EDX energy-dispersive X-ray emission spectroscopy
- the method of energy dispersive X-ray spectroscopy for material analysis uses the X-radiation emitted by a sample for the investigation of the elemental composition.
- the atoms in the sample are excited by means of an electron beam, which emit X-radiation with an element-specific energy.
- Fig. 7 shows a scanning electron micrograph of a cross section of the coating.
- the measurements were carried out with a Zeiss SEM DSM 962 with an acceleration voltage of 20 kV and about 500 magnification at a working distance of about 23 mm.
- the surface of the coating is a white thin layer with about 1-2 microns thickness, as a silicon oxide cover layer 111 recognizable.
- an approximately 20 ⁇ m thick intermediate layer which is formed mainly of silicon dioxide, aluminum, iron and oxygen.
- the substrate material 113 of the metallic component is arranged.
- Fig. 8-10 show spectra taken with a combination of the measurements of a SEM with an energy-dispersive X-ray emission analysis (EDX).
- EDX energy-dispersive X-ray emission analysis
- the above mentioned SEM was combined with an EDX (EDAX Genesis).
- the EDX has an energy resolution of 10 eV / ch and a count rate of about 14,000 pulses per second.
- Fig. 8 shows a spectrum of an examined area of the aforementioned coated profile piece, which specifically excluded from the coating and treated under the same conditions (500 ° C, 100 pyrolysis cycles of 1.5 h).
- the uncoated surface mainly contains iron (63%) and chromium (16%), as well as nickel (6.75%), manganese (1.85%), carbon (4.55%), oxygen (2.89%) , Aluminum (1.83%) and silicon (2.50%).
- the substrate material 113 of the metallic component is an alloy steel of the class of chrome steels.
- Fig. 9 shows a spectrum from the area of the intermediate layer 112. This area mainly comprises silicon (22.67%), oxygen (26.49%) iron (13.81%) and aluminum (13.86%), and nickel (2 , 05%), manganese (6.46%), carbon (11.02%) and chromium (3.64%).
- Fig. 9 shows a spectrum from the area of the silicon cover layer 111. This area mainly comprises silicon (35.6%), oxygen (28.05%) and aluminum (12.95%), and iron (4.73%), Nickel (0.92%), manganese (8.61%), carbon (8.50%) and chromium (0.63%).
- the silicon-containing intermediate layer of a thickness of, for example, 10-40 microns has at least 10% silicon and 10% of a metal, preferably aluminum, wherein the percentages relate to percentages by weight.
- inorganic-organic hybrid polymer coating according to the invention it is also possible with the inorganic-organic hybrid polymer coating according to the invention to ensure a transparent coating on metallic blanks, which has a high scratch resistance compared to uncoated components and at the same time the stainless steel color, partially even while avoiding tarnishing colors, reproduces.
- the measurement results also show a consistently low-noise mobility (classification 1-7, where 1 is defined as no noise and 7 as maximum noise).
- the forces which were used to pull out the coated pullout guide are in the range below 10 N, preferably between 3.0 to 4.5 N.
- the forces which were used for retracting the coated pullout guide are in the range below 11 N, preferably between 4.0 to 8 N.
- the coatings described are applied to a metallic component whose substrate material of steel number 1.4301 comprises a 18/10 chromium-nickel steel, steel of the material number 1.4016, a ferritic 17 percent chromium steel or steel of the material number 1.4310 a chromium nickel-alloyed steel.
- the coating offers particular advantages in high temperature applications, especially in ovens. However, it also offers advantages for components in Areas with high risk of corrosion. This includes, for example, the products of white goods, such as refrigerators and washing machines. Also furniture fittings are exposed during transport, especially in overseas transport, higher risk of corrosion, for example, by humid climate and / or seawater. In these areas, coated hardware has a longer life compared to uncoated hardware.
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Description
Die Erfindung betrifft ein Bauteil nach dem Oberbegriff des Anspruchs 1.The invention relates to a component according to the preamble of
Bei der Bereitstellung von Bauteilen, insbesondere metallischen Beschlägen, Seitengittern und Gargutträgern ist es bekannt, Bauteile aus selbst passivierenden nichtrostenden Stählen zu fertigen. Es erfolgt eine Oberflächenpassivierung meist bei einem Chromgehalt größer als 12 % wodurch sich eine Chromoxidschicht mit einer Stärke von 2-4 Nanometern ausbildet. Diese Passivschicht schützt das Bauteil vor Korrosion und verhindert den direkten Kontakt des Metalls mit einem anderen Medium. Die Passivierung durch eine Chromoxidschicht hat den Vorteil, selbsttätig passivierend zu sein, das heißt, dass beim Abtragen des Chromoxids durch Kratzer auf der Oberfläche, sich sofort wieder neues passivierendes Chromoxid aus der darunterliegenden Chromschicht bei Kontakt mit Luftsauerstoff bildet.In the provision of components, in particular metallic fittings, side rails and food supports, it is known to manufacture components from self-passivating stainless steels. There is a surface passivation usually at a chromium content greater than 12% which forms a chromium oxide layer with a thickness of 2-4 nanometers. This passive layer protects the component from corrosion and prevents direct contact of the metal with another medium. The passivation through a chromium oxide layer has the advantage of being passively self-activating, that is to say that when the chromium oxide is removed by scratches on the surface, new passivating chromium oxide forms immediately from the underlying chromium layer on contact with atmospheric oxygen.
Für die Bildung einer gleichmäßigen Passivschicht bei der Passivierung müssen jedoch neben dem Chromgehalt weitere Bedingungen erfüllt sein. Dies sind hauptsächlich eine metallisch reine Oberfläche und genügend Sauerstoff, um eine vollständige Oxidation entlang der Oberfläche zu gewährleisten. Sind diese Bedingungen nicht erfüllt, so kann sich bei hohen Temperaturen (Temperaturen ab 450 °C) keine spontane Oxidschicht bei selbst passivierenden nichtrostenden Stählen bilden, die Korrosionsbeständigkeit nimmt ab und es kommt zur Ausbildung einer porösen Chromoxidschicht in Folge von Verzunderung, welche nur noch geringen Korrosionsschutz ermöglicht. Daher erweist sich der Einsatz von selbst passivierenden nichtrostenden Stählen für die Fertigung von Bauteilen für Gar- und Backöfen im Anwendungsbereich ab 400 °C als unvorteilhaft.For the formation of a uniform passive layer during passivation, however, other conditions must be fulfilled in addition to the chromium content. These are mainly a metallically clean surface and enough oxygen to ensure complete oxidation along the surface. If these conditions are not met, then at high temperatures (temperatures from 450 ° C) can form no spontaneous oxide layer in self-passivating stainless steels, the corrosion resistance decreases and it leads to the formation of a porous chromium oxide layer due to scaling, which only small Corrosion protection possible. Therefore, the use of self-passivating stainless steels for the production of components for cooking and baking ovens in the application range from 400 ° C proves to be unfavorable.
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Es ist jedoch fraglich, ob die bisher genannten Beschichtungssysteme auch auf Bauteile mit einem breiten Anwendungsspektrum im Haushaltsbereich, also beispielsweise sowohl in Kühlschränken bei Temperaturen von -50 °C als auch in Pyrolyseöfen bei Temperaturen jenseits von 500 °C unter den dort vorherrschenden Korrosionsbedingungen einsetzbar sind.However, it is questionable whether the previously mentioned coating systems can also be used on components with a wide range of applications in the household sector, ie for example both in refrigerators at temperatures of -50 ° C and in pyrolysis ovens at temperatures beyond 500 ° C under the prevailing corrosion conditions ,
Die
Die
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Beschichtete Beschläge und Bauteile mit Anwendungsmöglichkeiten im Hochtemperaturbereich sind in der
Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren zu schaffen, welches die Beständigkeit von Bauteilen gegenüber Umwelteinflüssen, insbesondere beim Einsatz im Hochtemperaturbereich, verbessert.The object of the present invention is therefore to provide a method which improves the resistance of components to environmental influences, in particular when used in the high-temperature range.
Die vorliegende Erfindung löst diese Aufgabe durch ein Bauteil mit den Merkmalen des Anspruchs 1.The present invention solves this problem by a component having the features of
Das Verfahren zur Herstellung von Bauteilen insbesondere für Hochtemperaturanwendungen, sieht das Bereitstellen eines Rohteils vor, vorzugsweise durch Stanzen und Biegen eines Metallbleches, sowie das Aufbringen einer anorganisch-organischen Hybridpolymerschicht auf der Oberfläche des Rohteils, das Erhitzen des beschichteten Rohteils, beispielsweise auf eine Temperatur von mindestens 400 °C und das Abkühlen des beschichteten Rohteils auf Raumtemperatur. Dadurch wird ein Rohteil geschaffen, das eine gute Korrosionsbeständigkeit auch bei hohen Temperaturen aufweist. Bei der Beschichtung von Bauteilen für den Einsatz in Backöfen, Kühlschränke und dergleichen zeigte sich überraschenderweise erst nach einer thermischen Behandlung die zuvor mit einer anorganisch organischen Hybridpolymerschicht versehene Oberfläche als genügend widerstandsfähig, um den Belastungstests zu genügen.The method for manufacturing components, in particular for high temperature applications, provides for providing a blank, preferably by punching and bending a metal sheet, and applying an inorganic-organic hybrid polymer layer on the surface of the blank, heating the coated blank, for example to a temperature of at least 400 ° C and the cooling of the coated blank to room temperature. This creates a blank that has good corrosion resistance even at high temperatures. In the coating of components for use in ovens, refrigerators and the like, surprisingly, it was only after a thermal treatment that the surface previously provided with an inorganic-organic hybrid polymer layer proved sufficiently resistant to satisfy the stress tests.
Das Rohteil kann vorzugsweise aus Metall, beispielsweise aus Edelstahl, Stahl, Aluminium, Aluminiumlegierungen, Kupfer, Kupferlegierungen, Zink, Chrom oder Nickel bestehen. Die anorganisch-organische Hybridpolymerschicht kann jedoch auch auf Rohteile aufgebracht werden, welche bereits mit PTFE (Polytetrafluorethylen) oder PEEK (Polyetheretherketon) beschichtet sind. Auch auf LCP (liquid crystal polymer), Thermoplasten, Keramik und Emaille kann die Hybridpolymerschicht aufgebracht werden. Hierfür sind während des Herstellungsprozesses des Rohteils, in Abhängigkeit zu dessen Materialbeschaffenheit, verschiedenste Methoden der Formgebung anwendbar.The blank may preferably be made of metal, for example of stainless steel, steel, aluminum, aluminum alloys, copper, copper alloys, zinc, chromium or nickel. However, the inorganic-organic hybrid polymer layer can also be applied to blanks which are already coated with PTFE (polytetrafluoroethylene) or PEEK (polyetheretherketone). Also on LCP (liquid crystal polymer), thermoplastics, ceramics and enamel, the hybrid polymer layer can be applied. For this purpose, various methods of shaping are applicable during the manufacturing process of the blank, depending on its material properties.
Da die Schritte des Verfahrens auch automatisiert werden können, ist eine Anwendung in serieller Fertigung möglich. Die anorganisch-organische Hybridpolymerbeschichtung und anschließende thermische Behandlung bewirkt einen verbesserten Korrosionsschutz auch im höheren Temperaturbereich gegenüber der bisherigen Passivierung.Since the steps of the method can also be automated, an application in serial production is possible. The inorganic-organic Hybrid polymer coating and subsequent thermal treatment provides improved corrosion protection even in the higher temperature range compared to the previous passivation.
Nach einer anschließenden thermischen Behandlung zur Aushärtung bildet das entstandene Polymer eine harte Schicht, welche zudem reißfester ist, als dies beispielsweise beim Aufbringen eines rein anorganischen Materials der Fall wäre. Diese zusätzliche Festigkeit der Beschichtung in Folge der thermischen Behandlung macht sie daher resistenter gegenüber mechanischen Abriebs und sichert die wartungsfreie Nutzung der Bauteile, welche mit diesem Verfahren hergestellt wurden.After a subsequent thermal treatment for curing, the resulting polymer forms a hard layer, which is also more tear-resistant than would be the case, for example, when applying a purely inorganic material. This additional strength of the coating as a result of the thermal treatment therefore makes it more resistant to mechanical abrasion and ensures the maintenance-free use of the components produced by this method.
Es hat sich als vorteilhaft erwiesen, das anorganisch-organische Hybridpolymer durch ein Sol-Gel-Verfahren auf die Oberfläche des Rohteils aufzubringen. Durch die Hydrolyse werden dabei zunächst polare Gruppen geschaffen, welche den gelösten Ausgangsstoff in ein Sol umwandeln. Dieses viskose Sol wird bei geringem Materialverbrauch vollständig über die Oberfläche des Rohteils verteilt und haftet in Folge der Gelbildung fest an der Oberfläche des Rohteils an.It has proven advantageous to apply the inorganic-organic hybrid polymer to the surface of the blank by a sol-gel process. The hydrolysis initially creates polar groups which convert the dissolved starting material into a sol. This viscous sol is completely distributed with low material consumption over the surface of the blank and adheres due to the gel formation firmly on the surface of the blank.
Dabei kann vorzugsweise die besonders materialsparende und einfache Auftragungsart des Aufsprühens des Sols auf die Oberfläche des Rohteils angewendet werden.In this case, preferably the particularly material-saving and simple application method of spraying the sol onto the surface of the blank can be used.
Durch fluorhaltige Silane als Ausgangssubstanz für das Sol-Gel-Verfahren können die Oberflächen oleophobe und hydrophobe Eigenschaften erhalten, sie werden somit schmutzabweisend.By fluorine-containing silanes as a starting material for the sol-gel process, the surfaces oleophobic and hydrophobic properties can be obtained, they are thus dirt-repellent.
Ein vorteilhaftes Aushärten der Beschichtung sieht eine UV Bestrahlung vor, so dass in Folge von dreidimensionaler Vernetzung der Polymerschicht die Oberfläche kratzfest und resistenter gegenüber Abrieb wird. Daher kann das Rohteil nach diesem Schritt über längere Zeit gelagert werden, bevor es weiterverarbeitet wird.An advantageous curing of the coating provides UV irradiation, so that as a result of three-dimensional crosslinking of the polymer layer, the surface becomes scratch-resistant and more resistant to abrasion. Therefore, the blank can be stored for a long time after this step before it is further processed.
Bei geringeren Anforderungen an die Oberflächengüte können nach diesem Behandlungsschritt die behandelten Bauteile beispielsweise auch bei tiefen Temperaturen in Kühl- und / oder Gefriergeräten sowie in Backöfen bei Einsatztemperaturen zwischen -50-600 °C eingesetzt werden. Insbesondere beim Einsatz in Kühl- und Gefriergeräten kann somit auf die aufwendige höhere bzw. sogar zusätzliche Zinkauflage auf den Bauteilen verzichtet werden.With lower requirements on the surface quality, the treated components can, for example, even at low temperatures after this treatment step used in refrigerators, freezers and ovens at service temperatures between -50-600 ° C. In particular, when used in refrigerators and freezers can thus be dispensed with the expensive higher or even additional zinc coating on the components.
Es ist von Vorteil, dem Sol weitere anorganische Komponenten, beispielsweise SiO2 und/oder TiO2, zuzugeben, um durch Einbau dieser Komponenten in die anorganisch-organische Hybridpolymerstruktur während der Polymerisation eine zusätzliche Verbesserung der mechanischen Eigenschaften der Beschichtung zu erreichen.It is advantageous, the sol further inorganic components such as SiO 2 and / or TiO 2, add in order to achieve by incorporation of these components in the inorganic-organic hybrid polymer structure during polymerization, an additional improvement of the mechanical properties of the coating.
Weitere Zuschlagstoffe können aluminium- und/oder manganhaltige Verbindungen sein. Diese Verbindungen können während der Hydrolyse in die anorganisch-organische Hybridpolymerstruktur eingebunden werden. Nach einer thermischen Behandlung des Bauteils bei bis zu 800 °C kann Aluminium und/oder Mangan in das vorwiegend anorganische Netzwerk der Beschichtung eingebunden werden.Other additives may be aluminum and / or manganese compounds. These compounds can be incorporated into the inorganic-organic hybrid polymer structure during hydrolysis. After a thermal treatment of the component at up to 800 ° C, aluminum and / or manganese can be incorporated into the predominantly inorganic network of the coating.
Eine vorteilhafte Ausführungsform der Beschichtung sieht ein silizium- aluminium- und/oder titanhaltiges anorganisch-organisches Hybridpolymer vor, das bei Temperaturen bis zu 800 °C, vorzugsweise im Bereich von 400-600 °C, beständig ist. Aluminium-, Titan- und Silizium-Sauerstoffpolymerverbindungen sind kostengünstig, unkompliziert zu synthetisieren und chemisch resistent gegenüber einem Großteil von Chemikalien. Aufgrund ihrer Materialeigenschaften finden derartige Polymere vielerlei Anwendungen als Baumaterialien oder auch Beschichtungsmaterial und erfüllen somit die Anforderungen, welche an Beschichtungsmaterial für die Hochtemperaturanwendung gestellt werden.An advantageous embodiment of the coating provides a silicon-aluminum and / or titanium-containing inorganic-organic hybrid polymer, which at temperatures up to 800 ° C, preferably in the range of 400-600 ° C, is stable. Aluminum, titanium and silicon oxygen polymer compounds are inexpensive, easy to synthesize and chemically resistant to most chemicals. Due to their material properties, such polymers find many applications as building materials or even coating material and thus meet the requirements that are placed on coating material for high temperature application.
Die Wärmebehandlung der anorganisch-organischen Hybridpolymerbeschichtung erfolgt vorteilhafterweise nach einem Temperaturprogramm, wobei in einer Aufheizphase des beschichteten Rohkörpers zwei unterschiedliche Temperaturgradienten verwendet werden. Zunächst geschieht das langsame Hochheizen des Rohteils von Raumtemperatur ϑ0 =0-40 °C auf eine mittlere Temperatur ϑ1 von 80-200 °C. Anschließend erfolgt eine deutlich schnellere Aufheizphase, um die entsprechende Zieltemperatur ϑ2 zu erreichen. Somit wird der Beschichtung ermöglicht, sich bei der thermischen Ausdehnung des Rohteils auf die veränderten Bedingungen einzustellen und sich gegebenenfalls entlang der Substratoberfläche umzuorientieren. Das kontrollierte Aufheizen ist daher insofern von Vorteil, da ausgehärtete Beschichtungen im höheren Temperaturbereich zur Rissbildung neigen.The heat treatment of the inorganic-organic hybrid polymer coating is advantageously carried out according to a temperature program, two different temperature gradients being used in a heating phase of the coated green body. First, the slow heating of the blank occurs from room temperature θ 0 = 0-40 ° C to an average temperature θ 1 of 80-200 ° C. This is followed by a significantly faster heating phase in order to achieve the corresponding target temperature θ 2 . Thus, the coating is allowed at Adjust the thermal expansion of the blank to the changed conditions and, if necessary, to reorient along the substrate surface. The controlled heating is therefore advantageous in that hardened coatings tend to crack in the higher temperature range.
Das anorganisch-organisch hybridpolymerbeschichtete Rohteil wird vorzugsweise mindestens 20 Minuten, insbesondere mehr als 30 Minuten bei mindestens 200 °C, vorzugsweise 300-600 °C getempert. Dadurch wird eine haftfeste, korrosionsbeständige und weitgehend alterungsresistente Substrat-Polymerverbindung erreicht. In diesem Temperaturbereich erfolgt beispielsweise die Pyrolysereinigung eines Ofens. Die Zeit von mindestens 20 bzw. 30 Minuten ist von Vorteil, da bei dieser hohen Temperatur eine Oxidation der organischen Hybridpolymerbestandteile erfolgt, und somit nach der Oxidation der organischen Bestandteile eine feinverteiltere und reißfestere Polymerschicht entsteht, als bei Verwendung von ausschließlich anorganischen Ausgangsstoffen.The inorganic-organic hybrid polymer coated blank is preferably annealed for at least 20 minutes, more preferably for more than 30 minutes, at least 200 ° C, preferably 300-600 ° C. As a result, an adherent, corrosion-resistant and largely age-resistant substrate-polymer compound is achieved. In this temperature range, for example, the pyrolysis of a furnace. The time of at least 20 or 30 minutes is advantageous, since at this high temperature, an oxidation of the organic hybrid polymer components takes place, and thus after the oxidation of the organic components a finely divided and more tear-resistant polymer layer is formed, than when using only inorganic starting materials.
Während der Abkühlphase empfiehlt sich ein hoher Temperaturgradient von beispielsweise 5-40 K/min, vorzugsweise 15-25 K/min, wodurch sowohl die Materialbelastbarkeit an der Grenzfläche durch unterschiedliche thermische Ausdehnung minimiert und als auch Fehlordnungen im Material verhindert werden.During the cooling phase, a high temperature gradient of, for example, 5-40 K / min, preferably 15-25 K / min, is recommended, which minimizes the material loadability at the interface due to different thermal expansion and also prevents material misalignment.
In einer vorteilhaften Ausführungsform wird das beschichtete Rohteil bei einem Luftdurchsatz von 30-90 l/min, vorzugsweise 50-70 l/min getempert, wodurch eine möglichst vollständige Oxidation der organischen Anteile des Hybridpolymers auf der Substratoberfläche erreicht wird und eine spätere Exposition des Benutzers durch Verbrennungsprodukte einer eventuellen Nachverbrennung von organischen Polymeranteilen ausgeschlossen wird.In an advantageous embodiment, the coated blank is annealed at an air flow rate of 30-90 l / min, preferably 50-70 l / min, whereby as complete as possible oxidation of the organic moieties of the hybrid polymer is achieved on the substrate surface and subsequent exposure of the user by Combustion products of any post-combustion of organic polymer components is excluded.
Gemäß einer bevorzugten Ausführungsform wird das Bauteil vor dem Aufbringen der anorganisch-organischen Hybridpolymerschicht geglättet, um eine möglichst große Grenzfläche zwischen der sich bildendenden Polymeroberfläche und der Substratoberfläche zu erreichen und um zudem einen geringen Abstand zwischen beiden Oberflächen zu erhalten. Das Bauteil kann vor der Beschichtung eine Oberflächenrauhigkeit von maximal 500 nm, beispielsweise von 300 bis 500 nm, vorzugsweise 300 bis 400 nm aufweisen, was die Adhäsion des Polymers an der Substratoberfläche verbessert. Vor der Aufbringung der anorganisch-organischen Hybridpolymerschicht können Reinigungsverfahren wie z.B. eine Entfettung zum Einsatz kommen.According to a preferred embodiment, the component is smoothed before applying the inorganic-organic hybrid polymer layer in order to achieve the largest possible interface between the forming polymer surface and the substrate surface and also to obtain a small distance between both surfaces. The component may have a surface roughness of at most 500 nm, for example from 300 to 500 nm, preferably before coating 300 to 400 nm, which improves the adhesion of the polymer to the substrate surface. Prior to application of the inorganic-organic hybrid polymer layer, cleaning methods such as degreasing may be used.
Ein mit dem erfindungsgemäßen Verfahren hergestelltes Bauteil ist insbesondere in Backöfen im Hochtemperaturbereich einsetzbar, denn die Beschichtung bewirkt sowohl eine hohe Materialbelastbarkeit als auch eine hohe Temperaturbeständigkeit. In einem Backofen werden meist Lebensmittel gegart, die in der Regel viel Wasser enthalten, das verdunstet und sich an anderer Stelle niederschlägt. Dadurch ist bei Bauteilen in einem Backofen eine besondere Korrosionsanfälligkeit gegeben. Darüber hinaus sollte gerade in diesem Anwendungsbereich auf eine hygienisch hochwertige Verarbeitungsweise Wert gelegt werden.A component produced by the method according to the invention can be used in particular in ovens in the high temperature range, because the coating causes both a high material load capacity and a high temperature resistance. In an oven, food is usually cooked, which usually contains a lot of water, which evaporates and precipitates elsewhere. This is a special susceptibility to corrosion in components in an oven. In addition, especially in this application area should be placed on a hygienic quality processing value.
Des Weiteren kann ein nach dem erfindungsgemäßes Verfahren beschichtetes Bauteil als Beschlag in anderen Haushaltsgeräten im Bereich zwischen -50 °C bis 600 °C zum Einsatz kommen. Dies schließt u.a. auch den Einsatz in Kühlgeräten ein, wo besonders hohe Anforderungen an die Korrosionsbeständigkeit von Beschlägen, beispielsweise durch Salzsprühnebeltests und dergl., gestellt werden.Furthermore, a component coated by the method according to the invention can be used as a fitting in other domestic appliances in the range between -50 ° C. to 600 ° C. This includes u.a. also the use in refrigerators, where particularly high demands on the corrosion resistance of fittings, for example by salt spray tests and the like., Are provided.
Weiterhin kann das Bauteil insbesondere als Beschlag, wie z.B. als Scharnier, als Klappenbeschlag, als Schienensystem, als Gargutträger und als Auszugsführung, oder als Teil eines Beschlags ausgebildet sein.Furthermore, the component can be used in particular as a fitting, such as be designed as a hinge, as flap fitting, as a rail system, as a food support and as a pull-out guide, or as part of a fitting.
Die anorganisch-organische Hybridpolymerbeschichtung erhöht auch die Korrosionsbeständigkeit beim Transport der Bauteile, insbesondere die Beständigkeit gegen über äußere klimatische Einflüsse wie Regen, Schnee, Salzwasser, Seewassergischt und Nebel steigt. Container sind zwar gegen äußere Einflüsse geschützt, trotzdem kann sich im Inneren Kondensat bilden. Die aktuelle Temperatur sowie die Feuchtigkeit die beim Beladen in den Container gebracht wird, beeinflussen die jeweils aktuelle relative Luftfeuchte im Container. Die eingeschlossene Luft im Container, die Ladung, deren Verpackung oder das Staumaterial sind Feuchtigkeitsquellen. Erfindungsgemäß wird eine Beschichtung bereitgestellt, die die Korrosionsbeständigkeit, insbesondere beim Seetransport der beschichteten Bauteile erhöht. Des weiteren ist ein Einsatz der beschichteten Bauteile in Seewasserklima möglich. Weiterhin können die Bauteile, in Form von Möbelbeschlägen in Küchen- und/oder Labormöbeln eingesetzt werden die zur Lagerung von Reinigungsmitteln bzw. Chemikalien genutzt werden.The inorganic-organic hybrid polymer coating also increases the corrosion resistance during transport of the components, in particular the resistance to external climatic influences such as rain, snow, salt water, seawater spray and fog increases. Although containers are protected against external influences, condensate can nevertheless form inside. The current temperature and the moisture that is brought into the container during loading, affect the current relative humidity in the container. The trapped air in the container, the cargo, its packaging or the dunnage are sources of moisture. According to the invention, a coating is provided which is resistant to corrosion, in particular during sea transport of the coated components elevated. Furthermore, a use of the coated components in seawater climate is possible. Furthermore, the components can be used in the form of furniture fittings in kitchen and / or laboratory furniture used for the storage of cleaning agents or chemicals.
In die Beschichtung des Bauteils können zudem Farbstoffe und/oder Pigmenten eingearbeitet werden. Dies ist zum Erreichen von optischen Effekten von Vorteil, da mögliche Anlauffarben von Edelstählen farblich oder durch Metallicoptik kaschiert werden.In addition, dyes and / or pigments can be incorporated into the coating of the component. This is advantageous for achieving optical effects since possible tarnish colors of stainless steels are laminated in color or by metallic optics.
Falls das Bauteil bereits eine PTFE- oder PEEK-Beschichtung aufweist, auf welche die anorganisch-organische Hybridpolymerschicht aufgebracht wird, so können diese vorbeschichteten Bauteile bereits eingefärbt vorliegenIf the component already has a PTFE or PEEK coating to which the inorganic-organic hybrid polymer layer is applied, then these precoated components may already be colored
Das erfindungsgemäße Bauteil eignet sich besonders gut für die Herstellung einer Auszugsführung, insbesondere können die Schienen der Auszugsführung entsprechend beschichtet werden.The component according to the invention is particularly well suited for the production of a pullout guide, in particular, the rails of the pullout guide can be coated accordingly.
Die Erfindung wird nachfolgend anhand eines Ausführungsbeispieles mit Bezug auf die beigefügten Zeichnungen näher erläutert. Es zeigen:
- Fig. 1
- eine perspektivische Ansicht einer erfindungsgemäßen Auszugsführung;
- Fig. 2
- eine Explosionsdarstellung der Auszugsführung der
Figur1 ; und - Fig. 3
- ein schematisches Temperaturdiagramm für das Bereitstellen eines beschichteten Bauteils;
- Fig. 4
- eine Messwertetabelle mit Messwerten zur Zusammensatzung des Bauteils im Tiefenprofil von 0-100 µm;
- Fig. 5
- schematische Darstellung des Konzentrationsverlaufs einzelner Elemente im Tiefenprofil des beschichteten Bauteils
- Fig. 6
- Schichtdarstellung einer lichtmikroskopischen Bilddokumentation des beschichteten Bauteils;
- Fig. 7
- Schichtdarstellung einer rasterelektronenmikroskopischen Bilddokumentation des beschichteten Bauteils;
- Fig. 8a,b
- Darstellung einer Spektrenaufnahme und einer Messwerttabelle einer REM/EDX-Messung für einen unbeschichteten Abschnitt des Bauteils;
- Fig. 9a,b
- Darstellung einer Spektrenaufnahme und einer Messwerttabelle einer REM/EDX-Messung der Beschichtung des Bauteils; und
- Fig. 10a,b
- Darstellung einer Spektrenaufnahme und einer Messwerttabelle einer REM/EDX-Messung der Oberfläche des beschichteten Bauteils.
- Fig. 1
- a perspective view of a pullout guide according to the invention;
- Fig. 2
- an exploded view of the pullout guide of
Figur1 ; and - Fig. 3
- a schematic temperature diagram for the provision of a coated component;
- Fig. 4
- a measurement value table with measured values for the composition of the component in the depth profile of 0-100 μm;
- Fig. 5
- schematic representation of the concentration profile of individual elements in the depth profile of the coated component
- Fig. 6
- Layer representation of a light-microscopic image documentation of the coated component;
- Fig. 7
- Layer representation of a scanning electron microscopic image documentation of the coated component;
- Fig. 8a, b
- Representation of a spectra recording and a measurement table of a REM / EDX measurement for an uncoated portion of the component;
- Fig. 9a, b
- Representation of a spectral recording and a measured value table of a REM / EDX measurement of the coating of the component; and
- Fig. 10a, b
- Representation of a spectra image and a measurement table of a REM / EDX measurement of the surface of the coated component.
Die Schienen 1 bis 3 sind für den Einsatz in Backöfen aus einem gestanzten und gebogenen Stahlblech hergestellt und mit einer Beschichtung versehen. Die Herstellung der Bauteile der Auszugsführung, insbesondere der Schienen 1 bis 3 erfolgt durch die folgenden Schritte:The
Zunächst werden die metallischen Rohteile der Auszugsführung durch Stanzen und Biegen hergestellt. Das Rohteil kann dabei maschinell gefertigt werden. Dann wird eine anorganisch-organische Hybridpolymerschicht auf der Oberfläche der Rohteile aufgebracht.First, the metallic blanks of the pullout guide are made by punching and bending. The blank can be machined. Then, an inorganic-organic hybrid polymer layer is applied on the surface of the blanks.
Zuvor wird die Oberfläche der Rohteile vorbehandelt. Dies erfolgt im vorliegenden Beispiel durch Glättung der Oberfläche und durch chemische Reinigung verbleibender Fettreste durch basische Reinigungsmittel vorzugsweise bei pH= 8-10,5.Beforehand, the surface of the blanks is pretreated. This is done in the present example by smoothing the surface and by chemical cleaning of remaining fat residues by basic cleaning agents preferably at pH = 8-10.5.
Die beschichteten Rohteile werden dann auf eine Temperatur von mindestens 400 °C erhitzt und für eine vorbestimmte Zeitdauer getempert, bevor sie wieder auf Raumtemperatur abgekühlt werden.The coated blanks are then heated to a temperature of at least 400 ° C and annealed for a predetermined period of time before being recooled to room temperature.
Das Auftragen der anorganisch-organischen Hybridpolymerschicht erfolgt im Sol-Gel Verfahren, welches in
Hier werden Alkoxyverbindungen des Siliziums durch Hydrolyse unter Substition der Alkoxyfunktionen durch Hydroxygruppen in reaktive Silanole umgewandelt, die im Sol als kolloide Teilchen vorliegen. Diese Teilchen lagern sich beim Auftragen des Sols auf eine Oberfläche, vorzugsweise aus Metall, an dieser an. Durch Erwärmen werden die Wechselwirkungen zwischen Silanolmolekülen mit der Oberfläche weiter verstärkt bis hin zur Ausbildung von kovalenten Bindungen. Bei einer Erwärmung kommt es zudem zur Umwandlung des Sols in den Gelzustand unter Ausbildung von Polysiloxanen. Dabei werden Alkohole und Wasser in einer Kondensationsreaktion gebildet.Here, alkoxy compounds of silicon are converted by hydrolysis, with substitution of the alkoxy functions, by hydroxy groups into reactive silanols present in the sol as colloidal particles. These particles are deposited on the application of the sol on a surface, preferably of metal, at this. Heating further enhances the interaction of silanol molecules with the surface, leading to the formation of covalent bonds. When heated, it also leads to the transformation of the sol in the gel state to form polysiloxanes. In this case, alcohols and water are formed in a condensation reaction.
So treten beispielsweise in Alkoxyverbindungen des Siliziums und anderen Metallen- und Halbmetallen verschiedene Wechselwirkungen zwischen den organischen und anorganischen Bestandteilen der Hybridpolymere auf. Diese sind auf kovalente oder ionisch-kovalente Bindungen zurückzuführen.For example, in alkoxy compounds of silicon and other metals and semimetals, various interactions occur between the organic and inorganic components of the hybrid polymers. These are due to covalent or ionic-covalent bonds.
Die Beschichtungssole der anorganisch-organischen Hybridpolymere können in einem Sol-Gel Verfahren auf ein metallisches Bauteil flüssig appliziert werden und unter milden Reaktionsbedingungen anfließen und aushärten.The coating sols of the inorganic-organic hybrid polymers can be applied in liquid form to a metallic component in a sol-gel process and flow and harden under mild reaction conditions.
Dabei erfolgt während des Aushärtens eine basisch oder sauer katalysierte Hydrolyse der Alkoxide und im Anschluss die Ausbildung eines dreidimensionalen anorganischen Netzwerkes einer Siliziumoxidschicht, infolge einer Kondensationsreaktion.During the curing, a basic or acid-catalyzed hydrolysis of the alkoxides takes place, followed by the formation of a three-dimensional inorganic network of a silicon oxide layer as a result of a condensation reaction.
Anstelle des Siliziums als anorganische Komponente können beispielsweise auch Metalle, wie Zirkonium- oder Titanalkoxyverbindungen eingesetzt werden.Instead of silicon as the inorganic component, it is also possible, for example, to use metals such as zirconium or titanium alkoxy compounds.
Dabei können beispielsweise zu Tetramethoxysilan (TMOS) in Lösungsmittel (ca.1/4 des Volumens des TMOS) zunächst bei etwa 0 °C vorsichtig unter langsamer Zugabe (ca. 2 h) gelöst bzw. suspendiert werden. Die Zugabe erfolgt im Bereich zwischen 0-10 °C, da TMOS sehr leicht entzündlich, giftig und ätzend ist. Bei Temperaturen ab circa 20 °C können sich explosive Dampfgemische bilden. Anschließend wird zur Hydrolyse der organischen Verbindung konzentrierte wässrige HCl (etwa 1-3 Vol % gegenüber des Volumens des TMOS) über 30 min unter ständigem Rühren zugegeben. Dabei kann die HCl im Vorfeld auf eine Temperatur von etwa 0 °C heruntergekühlt werden. Anschließend wird das Rühren einige Minuten, beispielsweise 5-10 min, aufrecht erhalten. Durch Zugabe weiteren Lösungsmittels kann die Viskosität entsprechend eingestellt werden. Das Lösungsmittel kann protisch oder aprotisch polar, beispielsweise Isopropanol, sein.In this case, for example, to tetramethoxysilane (TMOS) in solvent (about 1/4 of the volume of the TMOS) initially at about 0 ° C carefully with slow addition (about 2 h) are dissolved or suspended. The addition is in the range between 0-10 ° C, since TMOS is very flammable, toxic and corrosive. At temperatures above 20 ° C explosive vapor mixtures can form. Subsequently, for the hydrolysis of the organic compound, concentrated aqueous HCl (about 1-3% by volume versus the volume of the TMOS) is added over 30 minutes with constant stirring. The HCl can be cooled down to a temperature of about 0 ° C in advance. Subsequently, the stirring is maintained for a few minutes, for example, 5-10 minutes. By adding additional solvent, the viscosity can be adjusted accordingly. The solvent may be protic or aprotic polar, for example isopropanol.
Alternativ kann auch eine Mischung aus hauptsächlich 3-Glycidyloxypropyltrimethoxysilan (GPTS) und Titantetraisopropylat unter basischen oder sauren Bedingungen durch Hydrolyse in eine fließfähige Beschichtungssubstanz umgewandelt und durch anschließendes Aushärten infolge von Kondensation bei 700-800 °C in eine anorganische Siliziumdioxidschicht umgewandelt werden.Alternatively, a mixture of mainly 3-glycidyloxypropyltrimethoxysilane (GPTS) and titanium tetraisopropylate may be converted into a flowable coating substance under basic or acidic conditions by hydrolysis and then converted into an inorganic silicon dioxide layer by subsequent curing as a result of condensation at 700-800 ° C.
Dabei bildet sich zwischen der oberen Siliziumdioxidschicht, mit einer Dicke von 0,1-2 µm und der Oberfläche des metallischen Bauteils eine Zwischenschicht, die zusätzlich zu dem Siliziumdioxid auch einen erhöhten Anteil an Metallverbindungen oder elementaren Metallen beispielsweise Chrom, Aluminium und/oder Mangan aufweist.In this case, an intermediate layer is formed between the upper silicon dioxide layer, with a thickness of 0.1-2 μm and the surface of the metallic component, which in addition to the silicon dioxide also forms an increased proportion of metal compounds or elemental metals such as chromium, aluminum and / or manganese.
Je nachdem, welche metallische Legierung das beschichtete Bauteil aufweist, kommt es zu Diffusionseffekten, bei denen das Silizium in die Metalloberfläche eindringt und zugleich einige Metallverbindungen in die Siliziumschicht eindiffundieren. Dabei kann das metallische Bauteil ggf. eine chrom- oder aluminiumhaltige Legierung aufweisen, bei welchen vornehmlich Aluminiumatome in die Siliziumschicht unter Ausbildung einer Zwischenschicht eindiffundieren.Depending on which metallic alloy the coated component has, it comes to diffusion effects, in which the silicon penetrates into the metal surface and at the same time diffuse some metal compounds into the silicon layer. In this case, the metallic component may optionally have a chromium- or aluminum-containing alloy in which predominantly aluminum atoms diffuse into the silicon layer to form an intermediate layer.
Die Diffusion von Chrom-, Mangan-, Aluminium- aber auch von Nickelverbindungen in der siliziumhaltigen Schicht ist dabei überraschenderweise größer als die Diffusion von Eisenverbindungen in diese Schicht. Dabei kann die Diffusion der Metallverbindungen durch einen Temperaturgradienten beim Aushärten vorteilhaft hinsichtlich der Eindringtiefe und Konzentrationsverteilung in der Schicht beeinflusst werden.The diffusion of chromium, manganese, aluminum but also nickel compounds in the silicon-containing layer is surprisingly greater than the diffusion of iron compounds in this layer. In this case, the diffusion of the metal compounds by a temperature gradient during curing can advantageously be influenced with regard to the penetration depth and concentration distribution in the layer.
Dabei kann das Metall, beispielsweise Aluminium, bereits als Bestandteil der anorganisch-organischen Hybridpolymerschicht eingebracht sein und sich in Folge von Diffusions- und Verteilungseffekten im Zentrum der Beschichtung ansammeln.In this case, the metal, for example aluminum, may already be incorporated as part of the inorganic-organic hybrid polymer layer and accumulate in the center of the coating as a result of diffusion and distribution effects.
Mangan kann aus dem Metall in die anorganisch-organische Hybridpolymerschicht während des Erhitzens eindiffundieren und sich in dieser Schicht anreichern.Manganese may diffuse from the metal into the inorganic-organic hybrid polymer layer during heating and accumulate in this layer.
Zudem können bei Temperaturen von 400-800 °C höhere Eindringtiefen insbesondere von Chrom-, Mangan- und Aluminiumatomen in die Siliziumschicht und der siliziumhaltigen Schicht in die metallische Oberfläche des Bauteils als dies bei niedrigeren Temperaturen der Fall ist erreicht werden.In addition, at temperatures of 400-800 ° C higher penetration depths of particular chromium, manganese and aluminum atoms in the silicon layer and the silicon-containing layer in the metallic surface of the component than at lower temperatures is the case can be achieved.
Durch den verringerten Eisengehalt in der Zwischenschicht kann sich eine passivierende Zwischenschicht ausbilden, welche ebenso wie die glasartige Silizium-Deckschicht auch bei über 500 °C temperaturbeständig ist.Due to the reduced iron content in the intermediate layer, a passivating intermediate layer can form, which, like the vitreous silicon cover layer, is temperature-resistant even at over 500.degree.
Die Integrität der Schicht bleibt auch erhalten, wenn man das derart beschichtete Bauteil kurzzeitig, also ca. 30 min einer Schweißflamme von 1000-1500 °C aussetzt. Somit kann die Beschichtung auch auf metallischen Bauteilen zumindest bereichsweise aufgebracht und verwendet werden, welche an einer unbeschichteten Oberfläche mit einer anderen metallischen Oberfläche verschweißbar sind. Falls hierbei die Schweißflamme in Berührung mit einem beschichteten Bereich des Beschlags kommt, so wird die Beschichtung nicht zerstört.The integrity of the layer is also retained if the component coated in this way is exposed to a welding flame of 1000-1500 ° C. for a short time, ie for about 30 minutes. Thus, the coating can be at least partially applied and used on metallic components, which are welded to an uncoated surface with another metallic surface. In this case, if the welding flame comes into contact with a coated area of the fitting, the coating is not destroyed.
Die Beschichtung kann ebenfalls nach dem Sol-Gel Verfahren auf eine chromierte Oberfläche aufgebracht werden, wobei die Chrom-Siliziumoxid-Beschichtung bei einem anschließenden Biegen des Bauteils, im Vergleich zu einer reinen chromierten Oberfläche erst bei höherer Belastung abblättert.The coating can also be applied to a chromed surface by the sol-gel method, wherein the chromium-silicon oxide coating does not flake off at higher load in a subsequent bending of the component, compared to a pure chromated surface.
Das Auftragen des flüssigen Sols auf die Oberfläche des metallischen Bauteils kann durch Sprühen, Tauchen, Bestreichen oder dergleichen erfolgen.The application of the liquid sol to the surface of the metallic component can be done by spraying, dipping, brushing or the like.
Durch UV-Behandlung können die organischen Bestandteile des anorganisch-organischen Hybridpolymers zusätzlich dreidimensional vernetzen, was der Beschichtung vorteilhafte mechanische Eigenschaften verleiht.By UV treatment, the organic constituents of the inorganic-organic hybrid polymer can additionally crosslink three-dimensionally, which gives the coating advantageous mechanical properties.
Zusätzlich zu den Siliziumatomen können weitere anorganische Komponenten, beispielsweise Titanoxid oder Siliziumoxid durch Umhüllung in eine Polysiloxanbeschichtung eingebaut werden, wodurch die mechanischen Eigenschaften der Beschichtung ebenfalls verbessert werden kann. Die weiteren anorganischen Komponenen können als feine Partikel, insbesondere im nanoskaligen Bereich zwischen 40 nm und 500 nm eingebaut werden.In addition to the silicon atoms, other inorganic components, for example, titanium oxide or silicon oxide may be incorporated by encapsulation in a polysiloxane coating, whereby the mechanical properties of the coating can also be improved. The further inorganic components can be incorporated as fine particles, in particular in the nanoscale range between 40 nm and 500 nm.
Um eine kratzfeste, alterungs- und korrosionsbeständige Beschichtung für den zu Hochtemperaturbereich zu schaffen, wird die anorganisch-organische Hybridpolymerschicht in Temperaturgradienten auf eine Temperatur in Bereich von 400-600 °C erhitzt, wobei die organischen Anteile des Polymers bevorzugt oxidiert werden. Somit wird durch das anorganisch-organische Hybridpolymer in Verbindung mit dem Sol-Gel Verfahren eine Netzwerkdichte geschaffen, welche geringe Schichtdicken, vorzugsweise zwischen 1,0-5,0 µm, beispielsweise einer auf Silizium basierten Polymerschicht und den Einbau von weiteren nanoskaligen anorganischen Komponenten als auch Farbstoffe oder Pigmente in die Polymerschicht ermöglichen.In order to provide a scratch resistant, aging and corrosion resistant coating for the high temperature region, the inorganic-organic hybrid polymer layer is heated in temperature gradients to a temperature in the range of 400-600 ° C, whereby the organic moieties of the polymer are preferentially oxidized. Thus, the inorganic-organic hybrid polymer in conjunction with the sol-gel process provides a network density which has low layer thicknesses, preferably between 1.0-5.0 μm, for example one on silicon based polymer layer and the incorporation of other nanoscale inorganic components as well as dyes or pigments in the polymer layer allow.
Die Temperzeit beträgt dabei zwischen 40 min und 3 h, vorzugsweise 1 h bei 200-800 °C, vorzugsweise 300-600 °C.The annealing time is between 40 minutes and 3 hours, preferably 1 hour at 200-800 ° C, preferably 300-600 ° C.
Diese Polymerschicht ist quarzartig, reißfest, mechanisch belastbar und schützt das Rohteil vor Korrosion. Zudem kaschiert sie Anlauffarben stahlhaltiger Materialien, beispielsweise als Metalliclackierung.This polymer layer is quartz-like, tear-resistant, mechanically resilient and protects the blank from corrosion. In addition, it conceals temper colors of steel-containing materials, for example as a metallic finish.
Die nachfolgende Tabelle zeigt verschiedene Versuchsreihen, bei welchen die Reinigungsfähigkeit von verschiedenen Bauteiloberflächen, welche nach den erfindungsgemäßen Verfahren beschichtet wurden, angegeben ist.
Die Oberflächen 1.4016 und 1.4301 sind dabei metallische Oberflächen von Auszugsführungen.The surfaces 1.4016 and 1.4301 are metallic surfaces of pullout guides.
Wie sich anhand aus der Tabelle ergibt, sind metallische Bauteile mit einer anorganisch-organischen Hybridpolymerbeschichtung bei 500 °C über längeren Zeitraum belastbar, so dass für derartige Bauteile der Einsatz im Hochtemperaturbereich ermöglicht ist. Hierbei ist jedoch nur eine eingeschränkte Reinigbarkeit der Auszugsführungen gegeben.As can be seen from the table, metallic components with an inorganic-organic hybrid polymer coating at 500 ° C for a longer period of time are resilient, so that for such components, the use in the high temperature range is possible. Here, however, only a limited cleanability of the pullout guides is given.
Die mit PEEK- beschichtete Auszugsführung des Versuchsablaufs 3 ist nicht über 2 h bei 500 °C belastbar, weist jedoch gegenüber den Beispielen 1 und 2 eine verbesserte Antihaftwirkung und Reinigung auf.The PEEK-coated pullout guide of the
Eine Sol-Gelbeschichtung in Verbindung mit einer PEEK-Beschichtung auf einer Auszugsführung ermöglicht vorteilhaft den Hochtemperatureinsatz als auch eine Verbesserung der Reinigbarkeit und somit die volle Pyrolysetauglichkeit.A sol-gel coating in conjunction with a PEEK coating on a pullout guide advantageously allows the high-temperature use as well as an improvement in the cleanability and thus the full Pyrolysetauglichkeit.
In
In dem dargestellten Ausführungsbeispiel wurde eine Auszugsführung beschrieben. Es ist natürlich auch möglich, andere Bauteile mit einer erfindungsgemäßen Beschichtung zu versehen.In the illustrated embodiment, a pullout guide has been described. Of course, it is also possible to provide other components with a coating according to the invention.
Das Reinigen der metallischen oder Kunststoff-Oberfläche des Rohteil vor dem Auftrag der anorganisch-organischen Hybridpolymerbeschichtung kann durch verschiedene mechanische und/oder chemische Reinigungsverfahren erfolgen. Des Weiteren kann eine zusätzliche Oberflächenbehandlung zum Aufrauen der Oberfläche erfolgen.The cleaning of the metallic or plastic surface of the blank prior to the application of the inorganic-organic hybrid polymer coating can be carried out by various mechanical and / or chemical cleaning methods. Furthermore, an additional surface treatment for roughening the surface can take place.
Beim Auftrag der anorganisch-organischen Hybridpolymerschicht kann das Fließverhalten derart eingestellt werden, dass sie selbst an senkrechten Flächen anhaftet.When applying the inorganic-organic hybrid polymer layer, the flow behavior can be adjusted so that it adheres even to vertical surfaces.
Das erfindungsgemäße Bauteil, mit der entsprechenden anorganisch-organischen Hybridpolymerbeschichtung hat die Vorteile der Kratzfestigkeit, der Abriebfestigkeit, des Korrosionsschutzes, der verbesserten Reinigungsfähigkeit, und der Verringerung der Schmutzanhaftung. Sie ist, anders als metallische Überzüge, transparent und kann auf ein eingefärbtes Substrat aufgebracht werden.The component according to the invention, with the corresponding inorganic-organic hybrid polymer coating, has the advantages of scratch resistance, abrasion resistance, corrosion protection, improved cleanability, and reduction of dirt adhesion. It is, unlike metallic coatings, transparent and can be applied to a colored substrate.
In
Die Messdaten in den
Das untersuchte Bauteil selbst ist ein nach dem erfindungsgemäßen Verfahren beschichtetes Profilstück einer Backofenauszugsführung. Das Bauteil wurde vor der Untersuchung mit 100 Pyrolysezyklen bei 500 °C über jeweils 1,5 h thermisch behandelt.The examined component itself is a profile piece of an oven extractor guide coated according to the method of the invention. The component was thermally treated with 500 pyrolysis cycles at 500 ° C for 1.5 hours prior to the test.
Die Tabelle der
Bei einer Schichtdicke von 1 µm besteht die Schicht überwiegend aus sauerstoffhaltigen Verbindungen. Dabei ist überwiegend Siliziumoxid mit einem Massenanteil von etwa 19 % vertreten. Dabei ist der Anteil an oxidischen Siliziumverbindungen etwa 1,6 fach höher als der Anteil der metallischen Oxide. Eisen ist mit einem Massenanteil von 2,6 % in diesem Bereich der Schicht enthalten.With a layer thickness of 1 μm, the layer consists predominantly of oxygen-containing compounds. In this case, predominantly silica with a mass fraction of about 19% is represented. The proportion of oxidic silicon compounds is about 1.6 times higher than the proportion of metallic oxides. Iron is contained in this area of the layer with a mass fraction of 2.6%.
Bei einer Schichtdicke von 2,5 µm hat der prozentuale Massenanteil der sauerstoffhaltigen Verbindungen, im Vergleich zur Zusammensetzung bei einer Schichtdicke von 1 µm, um etwa 10 % abgenommen. Der Massenanteil an Siliziumverbindungen liegt bei 24 %. Dabei ist der Massenanteil an Siliziumverbindungen nach wie vor 1,2 fach höher als der Massenanteil der metallischen Verbindungen. Dabei hat sich die Metallzusammensetzung gegenüber der Zusammensetzung der Schicht bei 1 µm verändert.At a layer thickness of 2.5 microns, the percentage by weight of oxygen-containing compounds, compared to the composition at a layer thickness of 1 micron, has decreased by about 10%. The mass fraction of silicon compounds is 24%. The mass fraction of silicon compounds is still 1.2 times higher than the mass fraction of the metallic compounds. In this case, the metal composition has changed compared to the composition of the layer at 1 micron.
Bei einem nahezu gleichbleibenden Eisenanteil sind die Chrom- und Nickelanteile um 3-4 % vermindert, wohingegen es zu einer Zunahme des Aluminiumanteils um einen Massenanteil von 5 %, des Mangananteils um 6 %, sowie einer Zunahme des Kupferanteils um 1,5 % kam.With an almost constant iron content, the chromium and nickel shares are reduced by 3-4%, whereas there was an increase of the aluminum content by 5% by mass, the manganese content by 6%, and an increase of copper by 1.5%.
Bei einer Schichtdicke um 10 µm beträgt der Massenanteil w (Aluminium) der Schicht 12,1 % und der Mangangehalt 11,1 %. Der Siliziummassenanteil liegt bei 20,9 %. Der Sauerstoffmassenanteil beträgt 33,3 %. Bemerkenswert ist dabei, dass der Eisenanteil gegenüber dem Aluminium- und Mangangehalt lediglich 6,6 % einnimmt.With a layer thickness of 10 μm, the mass fraction w (aluminum) of the layer is 12.1% and the manganese content is 11.1%. The silicon mass fraction is 20.9%. The oxygen mass fraction is 33.3%. It is noteworthy that the iron content compared to the aluminum and manganese content occupies only 6.6%.
Bei einer Schichtdicke von 15 µm beträgt der Eisenmassenanteil bereits 14,6 % und wächst im weiteren Profilverlauf bis auf etwa 70 % an.At a layer thickness of 15 microns, the iron mass fraction is already 14.6% and grows in the further profile profile up to about 70%.
Der Übergang der aluminium-, mangan- und siliziumreichen und eisenarmen Schicht in eine Eisen/Chromschicht erfolgt etwa bei 20 µm.The transition of the aluminum, manganese and silicon-rich and low-iron layer in an iron / chromium layer takes place at about 20 microns.
Die Zusammensetzung bei 100 µm gibt im Wesentlichen die elementare Zusammensetzung des eingesetzten Chromstahls wieder.The composition at 100 μm essentially reflects the elemental composition of the chromium steel used.
Zugleich bildet sich hinsichtlich der Siliziumkonzentration ein Konzentrationsplateau bei 15-17 % aus, welches sich über einen Bereich von 4 µm - 22 µm erstreckt.At the same time, a concentration plateau at 15-17% is formed with regard to the silicon concentration, which extends over a range of 4 μm-22 μm.
Im Bereich zwischen 20-50 µm ist ein Anstieg der Eisen und Chromkonzentration auf eine Konzentration von 73 % (für Eisen) bzw. 18 % (für Mangan) zu beobachten.In the range between 20-50 μm an increase of the iron and chromium concentration to a concentration of 73% (for iron) and 18% (for manganese) can be observed.
Wie sich überraschend gezeigt hat, erfolgte eine Diffusion und Verteilung von Aluminium- und Manganverbindungen in der siliziumhaltigen Schicht nach Auftrag der anorganisch-organischen siliziumhaltigen Hybridpolymerschicht im Sol-Gel Verfahren und einer Erhitzung der Beschichtung auf 550-800 °C, vorzugsweise 650-750 °C.As has surprisingly been found, a diffusion and distribution of aluminum and manganese compounds in the silicon-containing layer was carried out after application of the inorganic-organic silicon-containing hybrid polymer layer in the sol-gel Method and heating the coating to 550-800 ° C, preferably 650-750 ° C.
Durch die derart erhaltene zweilagige Beschichtung ergeben sich vielfältige Anwendungsmöglichkeiten. Durch die Einfärbung der Schicht kann die Oberfläche entsprechend den Kundenwünschen gestaltet werden. Eine Einebnung der Oberfläche durch Aufbringen der Beschichtung führt zu einer besseren Reinigbarkeit der Oberfläche und zu einer ansprechenden Optik.The two-layer coating thus obtained gives rise to a variety of possible applications. By coloring the layer, the surface can be designed according to the customer's wishes. A leveling of the surface by applying the coating leads to a better cleanability of the surface and to an attractive appearance.
Lediglich schemenhaft ist dabei die Siliziumoxid-Deckschicht 101 erkennbar.Only schematically is the silicon
Darunter ist die Zwischenschicht 102 angeordnet, welche neben Siliziumverbindungen vorwiegend Mangan- und Aluminiumverbindungen aufweist. Dabei weist die Schicht einen inhomogenen Aufbau auf, was durch eine Vielzahl dunklerer und hellerer Punkte in der grauen Schicht belegt wird. Diese Konzentrationsschwerpunkte sind jedoch kleiner und gleichmäßiger in der Schicht verteilt, als es bei der darunter angeordneten Stahlschicht 103 der Fall ist.Below this, the
Anhand der
Die folgenden Messwerte geben die Zusammensetzung der Oberfläche, also der Siliziumdioxid-Deckschicht als Massenanteile w (Substanz) in Prozent an:
- Silizium: 36,2 %, Sauerstoff: 35,4 %, Aluminium: 10,9 %, Mangan: 5,4 %, Eisen: 2,3 %, Kupfer: 4,0 %, Kalium: 0,7 %, Titan: 0,6 %,
4,0 %,Niob Natrium 0,7 0,1 %% und Kalzium
- Silicon: 36.2%, oxygen: 35.4%, aluminum: 10.9%, manganese: 5.4%, iron: 2.3%, copper: 4.0%, potassium: 0.7%, titanium : 0.6%, niobium 4.0%, sodium 0.7% and calcium 0.1%
Die Messwerte sind dabei die gemittelten Werte einer Dreifachmessung, wobei die Messwerte einer durchschnittlichen Schwankungsbreite von 5 %, bezogen auf den gemittelten Wert unterlagen.The measured values are the averaged values of a triple measurement, the measured values being subject to an average fluctuation range of 5%, based on the averaged value.
Die Messung erfolgte mittels energiedisperser Röntgenemissionsspektroskopie (EDX).The measurement was carried out by means of energy-dispersive X-ray emission spectroscopy (EDX).
Die Methode der energiedispersen Röntgenspektroskopie zur Materialuntersuchung nutzt die von einer Probe emittierte Röntgenstrahlung für die Untersuchung der Elementzusammensetzung. Dazu werden die Atome in der Probe mithilfe eines Elektronenstrahls angeregt, diese senden Röntgenstrahlung mit einer elementspezifischen Energie aus.The method of energy dispersive X-ray spectroscopy for material analysis uses the X-radiation emitted by a sample for the investigation of the elemental composition. For this purpose, the atoms in the sample are excited by means of an electron beam, which emit X-radiation with an element-specific energy.
Diese Messwertergebnisse der EDX stützen im Wesentlichen die Ergebnisse der Glühentladungsspektroskopie.These EDX measurement results essentially support the results of glow discharge spectroscopy.
Die Messungen wurden mit einem REM - DSM 962 von Zeiss mit einer Beschleunigungsspannung von 20 kV und etwa 500-facher Vergrößerung bei einem Arbeitsabstand von etwa 23 mm durchgeführt.The measurements were carried out with a Zeiss SEM DSM 962 with an acceleration voltage of 20 kV and about 500 magnification at a working distance of about 23 mm.
Dabei ist der Oberfläche der Beschichtung eine weiße dünne Schicht mit etwa 1-2 µm Dicke, als Siliziumoxid-Deckschicht 111 erkennbar.In this case, the surface of the coating is a white thin layer with about 1-2 microns thickness, as a silicon
Darunter angeordnet ist eine etwa 20 µm dicke Zwischenschicht die hauptsächlich aus Siliziumdioxid, Aluminium, Eisen und Sauerstoff gebildet ist.Arranged below is an approximately 20 μm thick intermediate layer which is formed mainly of silicon dioxide, aluminum, iron and oxygen.
Darunter ist das Substratmaterial 113 des metallischen Bauteils angeordnet.Below this, the
Die
Dabei wurde das oben aufgeführte REM mit einem EDX (EDAX Genesis) kombiniert. Das EDX hat dabei eine Energieauflösung von 10 eV/ch und eine Zählrate von ca. 14000 Impulse pro Sekunde.The above mentioned SEM was combined with an EDX (EDAX Genesis). The EDX has an energy resolution of 10 eV / ch and a count rate of about 14,000 pulses per second.
Somit handelt es sich bei dem Substratmaterial 113 des metallischen Bauteils um einen legierten Stahl aus der Klasse der Chromstähle.Thus, the
Diese Messwerte zeigen, dass die Silizium-Deckschicht überwiegend, also zu mehr als 50 %, aus oxidischen Silizium und Aluminiumverbindungen gebildet wird.These measured values show that the silicon covering layer is predominantly, ie more than 50%, formed from oxidic silicon and aluminum compounds.
Die siliziumhaltige Zwischenschicht einer Dicke von beispielsweise 10-40 µm weist mindestens 10% Silizium und 10% eines Metalls, vorzugsweise Aluminium, auf, wobei sich die prozentualen Abgaben auf Gewichtsprozente beziehen.The silicon-containing intermediate layer of a thickness of, for example, 10-40 microns has at least 10% silicon and 10% of a metal, preferably aluminum, wherein the percentages relate to percentages by weight.
Es ist mit der erfindungsgemäßen anorganisch-organischen Hybridpolymerbeschichtung zudem möglich, eine transparente Beschichtung auf metallischen Rohteilen zu gewährleisten, die eine hohe Kratzfestigkeit gegenüber unbeschichteten Bauteilen aufweist und zugleich die Edelstahlfarbe, z.T. auch unter Vermeidung von Anlauffarben, wiedergibt.It is also possible with the inorganic-organic hybrid polymer coating according to the invention to ensure a transparent coating on metallic blanks, which has a high scratch resistance compared to uncoated components and at the same time the stainless steel color, partially even while avoiding tarnishing colors, reproduces.
Zur Beurteilung der Funktionalität einer solchen transparenten Auszugsführung wurden 750 Laufintervalle nach den jeweiligen Pyrolysezyklen bei 500 °C durchgeführt. Dabei wurden folgende Prüfkriterien aufgestellt:
- a) Kraftaufwand beim Ausziehen der Auszugsführung (Fa) in N
- b) Kraftaufwand beim Einfahren der Auszugsführung (Fe) in N
- c) Laufgüte, beurteilt durch eine geschulte Prüfperson mittels Ordinalskala
- d) Geräusche, beurteilt durch eine geschulte Prüfperson mittels Ordinalskala
- a) force when pulling out the pullout guide (Fa) in N
- b) force when retracting the pullout guide (Fe) in N
- c) running quality, assessed by a trained examiner using ordinal scale
- d) noises, assessed by a trained examiner using ordinal scale
Die Laufgüte und Geräuschgüte einer beschichteten Auszugsführung nach 15 Pyrolysezyklen (500 °C) bei einer Prüflast von 10-15 kg wurde den Laufgüteklassen 1-3 zugeordnet.The running quality and sound quality of a coated pull-out guide after 15 pyrolysis cycles (500 ° C) at a test load of 10-15 kg was assigned to running grade classes 1-3.
Die Messergebnisse zeigten eine gleichbleibend gute Laufgüte (Klassifizierung 1-7, wobei 1 der höchsten Laufgüte und 7 der niedrigsten Laufgüte entspricht).The measurement results showed a consistently good runnability (classification 1-7, where 1 corresponds to the highest running quality and 7 to the lowest running quality).
Die Messergebnisse zeigen zudem eine gleichbleibend geräuscharme Beweglichkeit (Klassifizierung 1-7, wobei 1 als keine Geräuschentwicklung und 7 als höchstmögliche Geräuschentwicklung definiert ist.)The measurement results also show a consistently low-noise mobility (classification 1-7, where 1 is defined as no noise and 7 as maximum noise).
Die Kräfte, welche zum Ausziehen der beschichteten Auszugsführung angewandt wurden liegen dabei im Bereich unter 10 N, vorzugsweise zwischen 3,0 bis 4,5 N.The forces which were used to pull out the coated pullout guide are in the range below 10 N, preferably between 3.0 to 4.5 N.
Die Kräfte, welche zum Einfahren der beschichteten Auszugsführung angewandt wurden liegen im Bereich unter 11 N, vorzugsweise zwischen 4,0 bis 8 N.The forces which were used for retracting the coated pullout guide are in the range below 11 N, preferably between 4.0 to 8 N.
Bevorzugt werden die beschriebenen Beschichtungen auf ein metallisches Bauteil aufgebracht, dessen Substratmaterial aus Stahl der Werkstoffnummer 1.4301 einem 18/10 Chrom-Nickel-Stahl, Stahl der Werkstoffnummer 1.4016, einem ferritischen 17prozentigen Chromstahl oder Stahl der Werkstoffnummer 1.4310 einem chromnickellegierten Stahl umfasst.Preferably, the coatings described are applied to a metallic component whose substrate material of steel number 1.4301 comprises a 18/10 chromium-nickel steel, steel of the material number 1.4016, a ferritic 17 percent chromium steel or steel of the material number 1.4310 a chromium nickel-alloyed steel.
Die Beschichtung bietet besondere Vorteile in Hochtemperaturanwendungsbereichen, insbesondere in Backöfen. Sie bietet jedoch auch Vorteile bei Bauteilen in Bereichen mit hoher Korrosionsgefahr. Dies umfasst beispielsweise auch die Produkte der Weißen Ware, wie z.B. Kühlschränke und Waschmaschinen. Auch Möbelbeschläge sind beim Transport, insbesondere beim Übersee-Transport, höherer Korrosionsgefahr beispielsweise durch humides Klima und/oder Seewasser ausgesetzt. In diesen Gebieten haben beschichtete Beschläge gegenüber unbeschichteten Beschlägen eine längere Lebensdauer.The coating offers particular advantages in high temperature applications, especially in ovens. However, it also offers advantages for components in Areas with high risk of corrosion. This includes, for example, the products of white goods, such as refrigerators and washing machines. Also furniture fittings are exposed during transport, especially in overseas transport, higher risk of corrosion, for example, by humid climate and / or seawater. In these areas, coated hardware has a longer life compared to uncoated hardware.
- 11
- Führungsschieneguide rail
- 22
- Laufschienerunner
- 33
- Mittelschienemiddle rail
- 44
- Wälzkörperrolling elements
- 55
- WälzkörperkäfigRolling Element
- 66
- Laufbahnenraceways
- 101101
- Siliziumoxid-DeckschichtSilicon oxide topcoat
- 102102
- Zwischenschichtinterlayer
- 103103
- Stahlschichtsteel layer
- 111111
- Siliziumoxid-DeckschichtSilicon oxide topcoat
- 112112
- Zwischenschichtinterlayer
- 113113
- Substratmaterialsubstrate material
Claims (8)
- Guide rail, middle rail and/or running rail of a pull-out guide for high-temperature applications, in particular for the use in household appliances, characterized in that it has a coating produced by way of a method comprising the following steps:a) provision of a blank;b) applying an inorganic-organic hybrid polymer layer to a surface of the blank;c) heating the coated blank in order to cure the polymer layer, andd) cooling of the coated blank, wherein a metal compound or a metal diffuses into the hybrid polymer layer during heating of the coated blank for protection from corrosion,wherein the metal or metal compound comprises chromium, aluminum, manganese and/or nickel and
wherein the layer thickness of the coating is 10 to 40 µm. - Guide rail, middle rail and/or running rail of a pull-out guide according to claim 1, characterized in that the inorganic-organic hybrid polymer layer of the guide rail, middle rail and/or running rail contains a dye or pigments.
- Guide rail, middle rail and/or running rail of a pull-out guide according to claim 1 or 2, characterized in that the hybrid polymer layer has at least a mass fraction w of a metal of 7% for protection from corrosion.
- Guide rail, middle rail and/or running rail of a pull-out guide according to one of the claims 1 to 3, characterized in that the hybrid polymer layer has at least a mass fraction w of a metal of 12% for protection from corrosion.
- Guide rail, middle rail and/or running rail of a pull-out guide according to one of the claims 1 to 4, characterized in that the guide rail, middle rail and/or running rail comprise a metallic base body, an intermediate layer which is arranged above the base body and comprises silicon oxide and at least one metal and a cover layer with silicon oxide, wherein the intermediate layer made of silicon oxide and metal form a protection from corrosion of the substrate material in case of injury of the cover layer.
- Guide rail, middle rail and/or running rail of a pull-out guide according to claim 5, characterized in that the cover layer has a mass fraction w (silicon) of at least 30%.
- Guide rail, middle rail and/or running rail of a pull-out guide according to claim 6, characterized in that the cover layer has a mass fraction w (silicon) of at least 35%.
- Guide rail, middle rail and/or running rail of a pull-out guide according to one of the claims 1 to 7, characterized in that the layer thickness of the coating is 20 to 30 µm.
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DE102009044340A DE102009044340A1 (en) | 2008-12-02 | 2009-10-27 | Process for the production of components, in particular for high-temperature applications and components |
PCT/EP2009/066273 WO2010063776A1 (en) | 2008-12-02 | 2009-12-02 | Method for producing components for high temperature applications and metal component |
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DE102010016940A1 (en) * | 2010-05-12 | 2011-11-17 | Paul Hettich Gmbh & Co. Kg | Fitting and method for the production of a fitting |
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DE102011120736B4 (en) | 2011-02-01 | 2021-08-12 | Laag S.R.L. | Pull-out guide for an oven or for a dishwasher |
EP2699360A1 (en) | 2011-04-21 | 2014-02-26 | Paul Hettich GmbH & Co. KG | Metal component and method for the surface modification of a coated component |
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US6284682B1 (en) * | 1999-08-26 | 2001-09-04 | The University Of British Columbia | Process for making chemically bonded sol-gel ceramics |
US20030027011A1 (en) * | 2001-01-29 | 2003-02-06 | Nicholas Kotov | Organic/inorganic multilayer coating system |
JP2002348674A (en) * | 2001-05-24 | 2002-12-04 | Nisshin Steel Co Ltd | Aluminum plated steel sheet superior in solar radiation reflectivity |
US6617554B2 (en) * | 2001-09-28 | 2003-09-09 | Hearthware Home Products, Inc. | Counter-top electric cooker having a safety shut-off switch |
DE10155613A1 (en) * | 2001-11-13 | 2003-05-28 | Fraunhofer Ges Forschung | Process for coating surfaces using hybrid polymer materials |
DE10351467B4 (en) * | 2003-11-04 | 2011-07-07 | Schott Ag, 55122 | An article with an easily cleanable surface and process for its preparation |
DE102006003956A1 (en) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Production of a corrosion protection layer on a metal surface e.g. vehicle structure comprises applying a sol-gel composition to the metal surface, drying and/or hardening and applying a further layer and drying and/or hardening |
DE102007010955A1 (en) * | 2007-03-05 | 2008-09-11 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | coating composition |
-
2009
- 2009-10-27 DE DE102009044340A patent/DE102009044340A1/en not_active Withdrawn
- 2009-12-02 EP EP09764801.8A patent/EP2370211B1/en not_active Not-in-force
- 2009-12-02 KR KR1020117015466A patent/KR20110099125A/en not_active Application Discontinuation
- 2009-12-02 WO PCT/EP2009/066273 patent/WO2010063776A1/en active Application Filing
- 2009-12-02 JP JP2011538011A patent/JP5548994B2/en not_active Expired - Fee Related
- 2009-12-02 CN CN2009801482634A patent/CN102239011B/en not_active Expired - Fee Related
- 2009-12-02 US US13/132,331 patent/US20110236680A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CN102239011A (en) | 2011-11-09 |
US20110236680A1 (en) | 2011-09-29 |
KR20110099125A (en) | 2011-09-06 |
DE102009044340A1 (en) | 2010-06-10 |
JP5548994B2 (en) | 2014-07-16 |
JP2012510358A (en) | 2012-05-10 |
EP2370211A1 (en) | 2011-10-05 |
WO2010063776A1 (en) | 2010-06-10 |
CN102239011B (en) | 2013-10-23 |
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