EP1848839A2 - Protective layer against hot gas corrosion in the combustion chamber of an internal combustion engine - Google Patents

Protective layer against hot gas corrosion in the combustion chamber of an internal combustion engine

Info

Publication number
EP1848839A2
EP1848839A2 EP06706649A EP06706649A EP1848839A2 EP 1848839 A2 EP1848839 A2 EP 1848839A2 EP 06706649 A EP06706649 A EP 06706649A EP 06706649 A EP06706649 A EP 06706649A EP 1848839 A2 EP1848839 A2 EP 1848839A2
Authority
EP
European Patent Office
Prior art keywords
coating
piston
internal combustion
combustion engine
coating according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06706649A
Other languages
German (de)
French (fr)
Other versions
EP1848839B1 (en
Inventor
Günter BÜRKLE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KS Kolbenschmidt GmbH
Original Assignee
KS Kolbenschmidt GmbH
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Filing date
Publication date
Application filed by KS Kolbenschmidt GmbH filed Critical KS Kolbenschmidt GmbH
Publication of EP1848839A2 publication Critical patent/EP1848839A2/en
Application granted granted Critical
Publication of EP1848839B1 publication Critical patent/EP1848839B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2203/00—Non-metallic inorganic materials
    • F05C2203/08—Ceramics; Oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00—Other material characteristics; Treatment of material
    • F05C2253/12—Coating

Definitions

  • the invention relates to a coating of a tribologically highly resilient component of an internal combustion engine according to the features of the preamble of patent claim 1.
  • the invention is therefore based on the object to provide a coating of a tribologically highly resilient component from which results in a high temperature resistant corrosion protection layer for the component.
  • this object is achieved in that the coating is a ceramic coating of an organic-inorganic prepolymer, which is pyrolisierbar after application to the component.
  • the metals may be of the group Si (silicon), Ti (titanium), Zr (zirconium), Al (aluminum, Sn (tin) or Ce (cerium), although the list is not exhaustive (Pyrolysis) at temperatures in particular in the combustion chamber between 200 ° C and 450 ° C completely or partially converted into oxides and sintered together, so that the high temperature resistant protective layer is formed against hot gas corrosion.
  • a thin coating of the organic / inorganic prepolymer is applied to the component and then subjected to pyrolysis.
  • the particular advantage of the coating is on the one hand, that it is very thin, on the other hand, the baking process (pyrolysis) must not necessarily be made in the manufacture of the component, but can take place after installation of the component and its commissioning.
  • the coating in a piston of an internal combustion engine so the coating can be applied to the manufacturer of the piston, while the actual pyrolysis takes place only when the piston has been installed in the Brennkraftmaschi ⁇ e and this has been put into operation.
  • the coating is baked and provides a high temperature resistant protective layer of the piston crown against hot gas corrosion in the combustion chamber of the internal combustion engine, so that the life of the piston is significantly increased. It should be remembered in accordance with the invention that the entire piston crown, whether with or without combustion bowl, is provided with the coating according to the invention.
  • the piston has a Bren ⁇ raummulde, it can be thought that only the combustion bowl is completely coated or even the trough edge region of the combustion bowl, in order to effectively protect the there particularly claimed by the hot gas corrosion area.
  • the oxidation-resistant metallic particles mixed into the precursors may consist of Al, Cu, Fe, Cr, Ni or Co., the list also not being complete here.
  • an alloy of said metallic particles can be used, which serve to adjust the coefficient of thermal expansion and as a filler to avoid shrinkage cracks during pyrolysis.
  • the thermal expansion coefficient of the coating is adapted to the material of the component by the admixture of said materials and on the other hand, material stresses, in particular shrinkage cracks, effectively prevented.
  • color pigments are added to the coating. It goes without saying that the added color pigments are also heat resistant. For example, black or other dark pigments can be used to increase radiation absorption, resulting in improved heat radiation.
  • metallic pigments are added to the coating.
  • Such metallic pigments serve to increase the reflectance and also effectively prevent hot gas corrosion by reducing the component temperature.
  • the thermal expansion coefficients of the component and of the coating can also be adapted to one another by the metallic pigments, so that the thermal stresses between the coating and the component are reduced.
  • ceramic fillers are added to the coating. These ceramic fillers (in particular nanoparticles) increase the lubricity of the coating, so that not only prevents hot gas corrosion, but also reduces the friction of the coating.
  • the coating z. B. by spraying, dipping, knife coating or the like, is applied to the component. This is followed by drying, wherein either after drying the component is subjected to a heat treatment, whereby the coating is baked.
  • this may be waived by the manufacturer of the component, in particular the piston, namely, if the component is supplied to those who install it and then subjected to the heat treatment in the operating state. So it is the rule that a supplier of an automobile manufacturer produces pistons and then provides them with the coating according to the invention, which is initially only dried. If the piston supplied to the car manufacturer or to the manufacturer of the internal combustion engine, it can be installed, wherein the baking of the coating takes place at the first startup of the internal combustion engine. Further measures for the burn-in are then no longer required, then the high-temperature-resistant corrosion protection layer is available directly when the internal combustion engine is put into operation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Ceramic Engineering (AREA)
  • Nanotechnology (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Paints Or Removers (AREA)
  • Combustion Methods Of Internal-Combustion Engines (AREA)

Abstract

The invention relates to a coating for a tribologically highly loaded component., wherein said coating is embodied in the form of a ceramic coating made of an organic-inorganic prepolymer which is pyrolysed after being applied to the component.

Description

B E S C H R E I B U N G DESCRIPTION
Schutzschicht gegen Heißgaskorrosion im Verbrennungsraum einer BrennkraftmaschineProtective layer against hot gas corrosion in the combustion chamber of an internal combustion engine
Die Erfindung betrifft eine Beschichtung eines tribologisch hochbelastbaren Bauteils einer Brennkraftmaschine gemäß den Merkmalen des Oberbegriffes des Patentanspruchs 1.The invention relates to a coating of a tribologically highly resilient component of an internal combustion engine according to the features of the preamble of patent claim 1.
Die von heißen Verbrennungsgasen überstrichenen Flächen im Verbrennungsraum einer Brennkraftmaschine neigen grundsätzlich zu einer Oxidation. Davon betroffen sind insbe- sondere die Koibenböden der Kolben der Brennkraftmaschine, egai um welche Bauart von Kolben es sich handelt, ebenso kommt es zu diesen Oxidationen bei Stah!- und Leichtbaukolben. Aufgrund der resultierenden Heißgaskorrosion und der daraus resultierenden ther- mo-mechanischen Beanspruchung der Bereiche des Kolbenbodens, insbesondere der Randbereiche, wenn der Kolben eine Brennraummulde aufweist, kommt es zu Brüchen im Bereich des Kolbenbodens.The swept over by hot combustion gases surfaces in the combustion chamber of an internal combustion engine generally tend to oxidation. This affects in particular the Koibenböden of the piston of the internal combustion engine, egai which type of piston it is, as it comes to these oxidations in steel - and lightweight pistons. Due to the resulting hot gas corrosion and the resulting thermo-mechanical stress on the regions of the piston crown, in particular the edge regions, when the piston has a combustion bowl, fractures occur in the region of the piston crown.
Hiergegen sind schon Maßnahmen ergriffen worden, die allesamt bisher unzufriedenstellend sind. Aus der DE 196 29 399 A1 ist ein temperaturstabiler Hochtemperaturlack auf Basis von Polyphosphaten, Chromaten und Aluminiumpulver bekannt, der aber aufgrund von Umwelt- Schutzvorschriften schwierig in der Handhabung eines Produktionsprozesses ist. Aus der DE 40 03 038 C1 ist aus verschiedenen Materialien eine mehrlagige Schicht aus Grundschicht, Mittelschicht sowie Deckschicht bekannt, die bei der Produktion eines Kolbens nur aufwändig aufzubringen ist. Aus der DE 100 29 810 A1 sind plasmagespritzte Schichten bekannt, die ebenfalls produktionsaufwändig sind. Aus der DE 198 52 285 C2 ist es bekannt, durch ein entsprechendes Verfahren den Wärmeausdehnungskoeffizienten von Glas, Metall und Keramik anzupassen, wobei kein Bezug zu Brennkraftmaschinen genannt ist.Against this, measures have already been taken, all of which have so far been unsatisfactory. From DE 196 29 399 A1 a temperature-stable high-temperature lacquer based on polyphosphates, chromates and aluminum powder is known, but which is difficult to handle a production process due to environmental protection regulations. From DE 40 03 038 C1 a multilayer of base layer, middle layer and top layer is known from various materials, which is only consuming to apply in the production of a piston. From DE 100 29 810 A1 plasma sprayed layers are known, which are also expensive to produce. From DE 198 52 285 C2 it is known to adapt by a corresponding method, the thermal expansion coefficient of glass, metal and ceramic, wherein no relation to internal combustion engines is mentioned.
Der Erfindung liegt daher die Aufgabe zugrunde, eine Beschichtung eines tribologisch hochbelastbaren Bauteils bereitzustellen, aus der eine hochtemperaturfeste Korrosionsschutz- Schicht für das Bauteil resultiert. Erfindungsgemäß ist diese Aufgabe dadurch gelöst, dass die Beschichtung eine keramische Beschichtung aus einem organisch-anorganischen Präpolymer ist, der nach Aufbringung auf das Bauteil pyrolisierbar ist.The invention is therefore based on the object to provide a coating of a tribologically highly resilient component from which results in a high temperature resistant corrosion protection layer for the component. According to the invention, this object is achieved in that the coating is a ceramic coating of an organic-inorganic prepolymer, which is pyrolisierbar after application to the component.
Die Metalle können aus der Gruppe Si (Silicium), Ti (Titan), Zr (Zirkonium), AI (Aluminium, Sn (Zinn) oder Ce (Cer) sein, wobei die Aufstellung nicht vollständig ist. Diese Metalle werden im Verlauf des Einbrennens (Pyrolyse) bei Temperaturen insbesondere im Brennraum zwischen 200° C und 450° C vollständig oder teilweise in Oxide umgewandelt und miteinander versintert, so dass die hochtemperaturfeste Schutzschicht gegen Heißgaskorrosionen entsteht.The metals may be of the group Si (silicon), Ti (titanium), Zr (zirconium), Al (aluminum, Sn (tin) or Ce (cerium), although the list is not exhaustive (Pyrolysis) at temperatures in particular in the combustion chamber between 200 ° C and 450 ° C completely or partially converted into oxides and sintered together, so that the high temperature resistant protective layer is formed against hot gas corrosion.
Auf das Bauteil wird eine dünne Beschichtung aus dem organisch/anorganischen Präpolymer aufgebracht und anschließend einer Pyrolyse unterzogen. Der besondere Vorteil der Beschichtung ist einerseits, dass sie sehr dünn ist, andererseits muß der Einbrennprozeß (Pyrolyse) nicht zwangsweise bei der Herstellung des Bauteiles vorgenommen werden, sondern kann nach dem Einbau des Bauteils und dessen Inbetriebnahme stattfinden. Bei Anwendung der Beschichtung bei einem Kolben einer Brennkraftmaschine kann also die Beschichtung bei dem Hersteller des Kolbens aufgebracht werden, während die eigentliche Pyrolyse erst stattfindet, wenn der Kolben in die Brennkraftmaschiπe eingebaut und diese in Betrieb genommen worden ist. Nach den ersten Verbrennungen ist die Beschichtung eingebrannt und bietet eine hochtemperaturfeste Schutzschicht des Kolbenbodens gegen Heißgaskorrosionen im Verbrennungsraum der Brennkraftmaschine, so dass die Lebensdauer des Kolbens wesentlich gesteigert wird. Dabei ist in erfindungsgemäßer Weise daran zu denken, dass der vollständige Kolbenboden, egal ob mit oder ohne Brennraummulde, mit der erfindungsgemäßen Beschichtung versehen wird. Hat der Kolben eine Brenπraummulde, kann daran gedacht werden, dass nur die Brennraummulde vollständig beschichtet wird oder auch nur der Muldenrandbereich der Brennraummulde, um den dort besonders durch die Heißgaskorrosion beanspruchten Bereich wirksam zu schützen.A thin coating of the organic / inorganic prepolymer is applied to the component and then subjected to pyrolysis. The particular advantage of the coating is on the one hand, that it is very thin, on the other hand, the baking process (pyrolysis) must not necessarily be made in the manufacture of the component, but can take place after installation of the component and its commissioning. When applying the coating in a piston of an internal combustion engine so the coating can be applied to the manufacturer of the piston, while the actual pyrolysis takes place only when the piston has been installed in the Brennkraftmaschiπe and this has been put into operation. After the first burns, the coating is baked and provides a high temperature resistant protective layer of the piston crown against hot gas corrosion in the combustion chamber of the internal combustion engine, so that the life of the piston is significantly increased. It should be remembered in accordance with the invention that the entire piston crown, whether with or without combustion bowl, is provided with the coating according to the invention. The piston has a Brenπraummulde, it can be thought that only the combustion bowl is completely coated or even the trough edge region of the combustion bowl, in order to effectively protect the there particularly claimed by the hot gas corrosion area.
In der oxidischen Matrix können die in die Precursoren eingemischten oxidationsbeständigen metallischen Partikel aus AI, Cu, Fe, Cr, Ni oder Co bestehen, wobei auch hier die Aufzählung nicht vollständig ist. Außerdem ist eine Legierung aus den genannten metallischen Partikeln einsetzbar, die der Anpassung des Wärmeausdehnungskoeffizienten und als Füllstoff zur Vermeidung von Schrumpfungsrissen bei der Pyrolyse dienen. Damit wird durch die Beimischung dieser genannten Materialien einerseits der Wärmeausdehnungskoeffizient der Beschichtung an das Material des Bauteiles angepaßt und andererseits werden Materialspannungen, insbesondere Schrumpfungsrisse, wirksam verhindert. In Weiterbildung der Erfindung sind der Beschichtung Farbpigmente beigemischt. Dabei versteht es sich von selbst, dass die beigemischten Farbpigmente ebenfalls hitzebeständig sind. So können zum Beispiel schwarze oder sonstige dunkle Pigmente zur Erhöhung der Strahlungsabsorbtion verwendet werden, woraus eine verbesserte Wärmeabstrahlung resultiert.In the oxidic matrix, the oxidation-resistant metallic particles mixed into the precursors may consist of Al, Cu, Fe, Cr, Ni or Co., the list also not being complete here. In addition, an alloy of said metallic particles can be used, which serve to adjust the coefficient of thermal expansion and as a filler to avoid shrinkage cracks during pyrolysis. Thus, on the one hand, the thermal expansion coefficient of the coating is adapted to the material of the component by the admixture of said materials and on the other hand, material stresses, in particular shrinkage cracks, effectively prevented. In a further development of the invention, color pigments are added to the coating. It goes without saying that the added color pigments are also heat resistant. For example, black or other dark pigments can be used to increase radiation absorption, resulting in improved heat radiation.
In Weiterbildung der Erfindung sind der Beschichtung metallische Pigmente beigemischt. Solche metallischen Pigmente dienen der Erhöhung des Reflexionsgrades und verhindern durch die Verringerung der Bauteiltemperatur ebenfalls wirksam eine Heißgaskorrosion. Außerdem lassen sich auch durch die metallischen Pigmente die Wärmeausdehnungskoeffizienten des Bauteiles und der Beschichtung aneinander anpassen, so dass die thermischen Spannungen zwischen der Beschichtung und dem Bauteil abgebaut werden.In a further development of the invention, metallic pigments are added to the coating. Such metallic pigments serve to increase the reflectance and also effectively prevent hot gas corrosion by reducing the component temperature. In addition, the thermal expansion coefficients of the component and of the coating can also be adapted to one another by the metallic pigments, so that the thermal stresses between the coating and the component are reduced.
In Weiterbildung der Erfindung sind der Beschichtung keramische Füllstoffe (Partikel) beigemischt. Diese keramischen Füllstoffe (insbesondere Nanopartikel) erhöhen die Gleitfähigkeit der Beschichtung, so dass nicht nur Heißgaskorrosionen verhindert, sondern auch die Reibung der Beschichtung herabgesetzt werden.In a further development of the invention, ceramic fillers (particles) are added to the coating. These ceramic fillers (in particular nanoparticles) increase the lubricity of the coating, so that not only prevents hot gas corrosion, but also reduces the friction of the coating.
In einer weiteren Ausgestaltung der Erfindung können auch mehrere der vorgenannten Pigmentarten miteinander kombiniert werden.In a further embodiment of the invention, several of the aforementioned types of pigment can be combined.
'Ein einfacher und kostengünstiger Herstellungsprozeß besteht darin, dass die Beschichtung z. B. durch Spritzen, Tauchen, Rakeln oder dergleichen, auf das Bauteil aufgebracht wird. Anschließend erfolgt eine Trocknung, wobei entweder nach dem Trocknen das Bauteil einer Hitzebehandlung unterzogen wird, wodurch die Beschichtung eingebrannt wird. Hierauf kann allerdings beim Hersteller des Bauteiles, insbesondere des Kolbens, verzichtet werden, wenn nämlich das Bauteil an denjenigen geliefert wird, der es einbaut und im Betriebszustand dann der Hitzebehandlung unterzogen wird. So ist es der Regelfall, dass ein Zulieferer eines Automobilherstellers Kolben herstellt und diese dann mit der erfindungsgemäßen Beschichtung versieht, die zunächst nur eingetrocknet ist. Wird der Kolben an den Automobilhersteller bzw. an den Hersteller der Brennkraftmaschine geliefert, kann er eingebaut werden, wobei das Einbrennen der Beschichtung bei der ersten Inbetriebnahme der Brennkraftmaschine erfolgt. Weitere Maßnahmen für das Einbrennen sind dann nicht mehr erfor- derlich, so dann direkt mit Inbetriebnahme der Brennkraftmaschine die hochtemperaturfeste Korrosionsschutzschicht zur Verfügung steht. 'A simple and inexpensive manufacturing process is that the coating z. B. by spraying, dipping, knife coating or the like, is applied to the component. This is followed by drying, wherein either after drying the component is subjected to a heat treatment, whereby the coating is baked. However, this may be waived by the manufacturer of the component, in particular the piston, namely, if the component is supplied to those who install it and then subjected to the heat treatment in the operating state. So it is the rule that a supplier of an automobile manufacturer produces pistons and then provides them with the coating according to the invention, which is initially only dried. If the piston supplied to the car manufacturer or to the manufacturer of the internal combustion engine, it can be installed, wherein the baking of the coating takes place at the first startup of the internal combustion engine. Further measures for the burn-in are then no longer required, then the high-temperature-resistant corrosion protection layer is available directly when the internal combustion engine is put into operation.

Claims

Patentansprüche claims
1. Beschichtung eines tribologisch hoch belastbaren Bauteils, dadurch gekennzeichnet, dass die Beschichtung eine keramische Beschichtung aus einem organisch-anorganischen Präpolymer ist, das nach Aufbringung auf das Bauteil pyrolysierbar ist.1. coating a tribologically highly resilient component, characterized in that the coating is a ceramic coating of an organic-inorganic prepolymer, which is pyrolysable after application to the component.
2. Beschichtung nach Anspruch 1 , dadurch gekennzeichnet, dass die Beschichtung aus einbrennbaren Metall-Alkoxiden und/oder polymerisierbaren organometallischen Verbindungen in organischen Lösungsmitteln hergestellbar ist.2. Coating according to claim 1, characterized in that the coating of combustible metal alkoxides and / or polymerizable organometallic compounds in organic solvents can be produced.
3. Beschichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Beschichtung metallische Pigmente beigemischt sind.3. Coating according to claim 1 or 2, characterized in that the coating metallic pigments are mixed.
4.4th
Beschichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Beschichtung Farbpigmente beigemischt sind.Coating according to claim 1 or 2, characterized in that the coating color pigments are mixed.
5.5th
Beschichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Beschichtung keramische Partikel, insbesondere Nanopartikel, beigemischt sind.Coating according to claim 1 or 2, characterized in that the coating ceramic particles, in particular nanoparticles, are admixed.
6.6th
Beschichtung nach einem der Anspruch 3, 4 oder 5, dadurch gekennzeichnet, dass die Beschichtung zumindest zwei der Pigmentarten beigemischt sind.Coating according to one of claims 3, 4 or 5, characterized in that the coating is admixed with at least two of the pigment types.
7.7th
Kolben einer Brennkraftmaschine, gekennzeichnet durch eine Beschichtung gemäß einem der vorhergehenden Ansprüche eines Kolbenbodens des Kolbens. Piston of an internal combustion engine, characterized by a coating according to one of the preceding claims of a piston crown of the piston.
8.8th.
Kolben einer Brennkraftmaschine, gekennzeichnet durch eine Beschichtung gemäß einem der vorhergehenden Ansprüche zumindest eines Muldenrandes einer in einem Kolbenboden des Kolbens vorhandenen Brennraummulde.Piston of an internal combustion engine, characterized by a coating according to one of the preceding claims at least one trough edge of a present in a piston head of the piston combustion bowl.
9.9th
Kolben nach Anspruch 8 einer Brennkraftmaschine, gekennzeichnet durch eine Beschichtung gemäß einem der vorhergehenden Ansprüche der vollständigen Brennraummulde. Piston according to claim 8 of an internal combustion engine, characterized by a coating according to one of the preceding claims of the complete combustion bowl.
EP06706649A 2005-02-15 2006-02-04 Protective layer against hot gas corrosion in the combustion chamber of an internal combustion engine Not-in-force EP1848839B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005006671A DE102005006671A1 (en) 2005-02-15 2005-02-15 Protective layer against hot gas combustion in the combustion chamber of an internal combustion engine
PCT/EP2006/000991 WO2006087114A2 (en) 2005-02-15 2006-02-04 Protective layer against hot gas corrosion in the combustion chamber of an internal combustion engine

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EP (1) EP1848839B1 (en)
JP (1) JP2008533349A (en)
AT (1) ATE527395T1 (en)
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WO (1) WO2006087114A2 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008034428B4 (en) * 2008-07-24 2011-06-16 Ks Kolbenschmidt Gmbh Method for producing a piston of an internal combustion engine
KR101993684B1 (en) * 2011-10-31 2019-06-27 테네코 인코퍼레이티드 Coated piston and a method of making a coated piston
WO2013080389A1 (en) * 2011-12-02 2013-06-06 日本碍子株式会社 Engine combustion chamber structure
WO2013125704A1 (en) * 2012-02-22 2013-08-29 日本碍子株式会社 Engine combustion chamber structure and inner wall structure of flow path
JPWO2013129430A1 (en) * 2012-02-27 2015-07-30 日本碍子株式会社 Thermal insulation member and engine combustion chamber structure
JP5904425B2 (en) 2014-03-27 2016-04-13 スズキ株式会社 Anodized film, treatment method thereof, and piston for internal combustion engine
JP6418498B2 (en) * 2014-03-27 2018-11-07 スズキ株式会社 Anodizing method and structure of internal combustion engine
DE102014224830B4 (en) * 2014-12-04 2022-10-20 Volkswagen Aktiengesellschaft internal combustion engine and motor vehicle
WO2017174143A1 (en) 2016-04-08 2017-10-12 Volvo Truck Corporation A piston for a cylinder for an internal combustion engine
DE102021210995A1 (en) * 2021-09-30 2023-03-30 Federal-Mogul Nürnberg GmbH Anti-oxidation layer for engine pistons made of steel or an iron-based alloy

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3038458A (en) * 1959-10-09 1962-06-12 British Internal Combust Eng Internal combustion engines and pistons therefor
US3356515A (en) * 1965-12-27 1967-12-05 Exxon Research Engineering Co High temperature protective coating
DE3404284A1 (en) * 1984-02-08 1985-08-08 Kolbenschmidt AG, 7107 Neckarsulm PISTON FOR INTERNAL COMBUSTION ENGINES
JPS61192842A (en) * 1985-02-21 1986-08-27 Miyama Kogyo Kk Ceramic polymerization engine
JPH0620638B2 (en) * 1985-10-14 1994-03-23 トヨタ自動車株式会社 Adiabatic piston manufacturing method
US5169912A (en) * 1989-01-19 1992-12-08 Keehan Donald J Metallic oxide-oxirane polymers and prepolymers
DE4003038C1 (en) * 1990-02-02 1990-08-09 Mtu Muenchen Gmbh
US5182143A (en) * 1990-02-28 1993-01-26 Lord Corporation Layered sol-gel coatings
DE4016723A1 (en) * 1990-05-24 1991-11-28 Kolbenschmidt Ag PISTON CONNECTING ROD ARRANGEMENT
US5805973A (en) * 1991-03-25 1998-09-08 General Electric Company Coated articles and method for the prevention of fuel thermal degradation deposits
JPH05231538A (en) * 1992-02-17 1993-09-07 Shima Boeki Kk Ceramic-coated piston for internal combustion engine
US5305726A (en) * 1992-09-30 1994-04-26 United Technologies Corporation Ceramic composite coating material
JPH07109580A (en) * 1993-10-12 1995-04-25 Isuzu Motors Ltd Sliding member and its production
AU1297095A (en) * 1993-12-06 1995-06-27 White Eagle International Technologies, L.P. Process for preparation of high temperature composite ceramic materials and coating
DE19629399B4 (en) * 1996-07-20 2008-10-16 Mahle Gmbh Piston for internal combustion engines with a piston crown or piston top
DE59807355D1 (en) * 1997-05-12 2003-04-10 Fraunhofer Ges Forschung Composition for high-temperature resistant, pyrolytic ceramic coatings
WO1999003939A1 (en) * 1997-07-16 1999-01-28 Kansai Paint Co., Ltd Thermosetting, high-solid coating composition and method of forming topcoating by using the same
DE19843581C2 (en) * 1998-09-23 2002-11-14 Basf Coatings Ag Process for the production of coated substrates and correspondingly coated substrates and their use
US6284682B1 (en) * 1999-08-26 2001-09-04 The University Of British Columbia Process for making chemically bonded sol-gel ceramics
WO2001029139A1 (en) * 1999-10-21 2001-04-26 Dow Global Technologies Inc. Inorganic/organic compositions
US6630244B1 (en) * 2001-03-23 2003-10-07 Delavan Inc. Carbon resistant surface coating
EP1156024A1 (en) * 2000-05-19 2001-11-21 "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." Composite ceramic precursors and layers
DE10029810A1 (en) * 2000-06-16 2001-12-20 Mahle Gmbh Piston for diesel engine; has steel base with combustion mould and has thermal sprayed NiCrAl, CoCrAl or FeCrAl alloy coating, which is thicker at mould edge
JP2002275637A (en) * 2001-03-22 2002-09-25 Nagase & Co Ltd Engine parts and method for manufacturing the same
JP2004529057A (en) * 2001-05-18 2004-09-24 カール−ツァイス−スティフツング Coatings that clean easily
DE10130673A1 (en) * 2001-06-28 2003-01-23 Volkswagen Ag Internal combustion engine
ATE269913T1 (en) * 2002-07-31 2004-07-15 Itn Nanovation Gmbh CERAMIC COATING FOR COMBUSTION BOILERS
US7601425B2 (en) * 2003-03-07 2009-10-13 The Curators Of The University Of Missouri Corrosion resistant coatings containing carbon
US7383807B2 (en) * 2005-05-23 2008-06-10 Federal-Mogul World Wide, Inc. Coated power cylinder components for diesel engines
US7802553B2 (en) * 2005-10-18 2010-09-28 Gm Global Technology Operations, Inc. Method to improve combustion stability in a controlled auto-ignition combustion engine
US7458358B2 (en) * 2006-05-10 2008-12-02 Federal Mogul World Wide, Inc. Thermal oxidation protective surface for steel pistons
US8789308B2 (en) * 2008-06-17 2014-07-29 Bass Pro Intellectual Property, L.L.C. Fishing lure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006087114A3 *

Also Published As

Publication number Publication date
DE102005006671A1 (en) 2006-08-17
WO2006087114A3 (en) 2008-09-12
ATE527395T1 (en) 2011-10-15
US20120180748A1 (en) 2012-07-19
JP2008533349A (en) 2008-08-21
WO2006087114A2 (en) 2006-08-24
US20080149897A1 (en) 2008-06-26
EP1848839B1 (en) 2011-10-05

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