EP2134885B1 - Revêtement d'un composant en acier trempé et procédé d'application du revêtement - Google Patents

Revêtement d'un composant en acier trempé et procédé d'application du revêtement Download PDF

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Publication number
EP2134885B1
EP2134885B1 EP08717034.6A EP08717034A EP2134885B1 EP 2134885 B1 EP2134885 B1 EP 2134885B1 EP 08717034 A EP08717034 A EP 08717034A EP 2134885 B1 EP2134885 B1 EP 2134885B1
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Prior art keywords
sol
laser
process according
gel
coating
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English (en)
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EP2134885A1 (fr
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Bertram Haag
Walter Holweger
Tim Matthias Hosenfeldt
Yashar Musayev
Jürgen WINDRICH
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Schaeffler Technologies AG and Co KG
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Schaeffler Technologies AG and Co KG
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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

Definitions

  • the invention is in the field of coating tribologically and / or by chemical corrosion stressed components, which consist of hardened steel.
  • the present invention is basically applicable to many different types of hardened steel components that are subject to abrasive wear or other corrosive effects.
  • the corresponding components themselves should consist of simple hardened steel, such as bearing steel, 16MnCr5, C45, 100Cr6, 31CrMoV9, 80Cr2 or similar, and be surface hardened.
  • Some of the requirements may be met in some cases by coatings of a specific nature, such as hardness or low frictional resistance, but regularly suffer from other characteristics of the tribological system.
  • thermo-chemical processes such as in plasma nitrocarburizing
  • any provided bonding layers having a relatively high hardness on the steel parts only have a slight hold, so that the possible bonding layer may undesirably come off the substrate ,
  • problems can occur due to the shape and size of the components to be coated, which complicate the coating, for example, if the components are very small, especially for bearings below an inner diameter of 75 mm or not cylindrically, since in these cases, a spray coating process difficult is.
  • the thinness of components to be coated can complicate the coating, since stresses can occur that can lead to distortion of the components.
  • a wear-resistant coating is additionally electrically insulating. This is the case, for example, when a mechanical device, which is to be coated wear-resistant, is connected or coupled to an electronic device for measurement or control. Often, for example, rotary bearings can be used for potential separation. For this purpose, high-strength and wear-resistant, electrically insulating materials are necessary.
  • Such a sol-gel coating has the advantage that it can be applied without force and without temperature change by dipping, spraying or a spinning process and later sintered. Thus, the risks of a mechanical Delay minimized.
  • the layer thickness can be well controlled and a high uniformity of the coating can be ensured.
  • Corresponding dipping processes require a slow and uniform extraction of the component from the sol.
  • the coating according to the invention also an electrical insulation of components, such as bearings and mechatronic components with thin ceramic layers can be realized
  • the prerequisite for maintaining the good mechanical properties of the component is, however, that the tempering temperatures of the hardened steels, which are for example at about 180 to 220 degrees Celsius, are not exceeded at the component surface during sintering of the sol-gel layer, so that the hardened Structure in the steel is preserved.
  • Annealing is understood to mean heating the steel after curing to a temperature between room temperature and lower transformation point Ac1 and holding at that temperature followed by cooling.
  • the temperature of the component must be kept below a temperature at which annealing takes place to a considerable extent, that is, for example, below 180 or 200, or 220 degrees Celsius.
  • a microstructure transformed by rapid cooling is not in a stable equilibrium, so that the hardness can be reduced again by reheating with a simultaneous increase in toughness.
  • the degree of hardness decrease is determined by the tempering temperature and tempering time. Therefore, the invention provides the method of laser sintering which enables good temperature control with high temperature gradients within the coating during the process.
  • the sol-gel process which is known per se for other applications will first be described in more detail, which according to the invention is applied to the tribologically stressed steel parts.
  • the application is out of the DE69919805T2 according to the sol-gel layers are applied to a plastic sub-material and sintered by means of laser pulses. There, by targeted heating of the lower material, this partially liquefied or at least softened to obtain an optimized connection with the applied ceramic sintered layer.
  • the starting point of the sol-gel process is in each case a liquid sol, which is converted by a sol-gel transformation into a solid gel state.
  • Sols are dispersions of solid particles in the size range between 1 nm and 100 nm, dispersed in water or dissolved in organic solvents.
  • the sol-gel process is used to produce ceramic or ceramic-organic materials. This method is used for the production of layers and bodies of nanocrystalline or ceramic nature or ceramic fibers and for the coating of components.
  • the starting point of sol-gel processes are often also sol systems with organometallic polymers.
  • the transformation takes place from the liquid sol via a gel state to the ceramic or organoceramic material.
  • a 3-dimensional crosslinking takes place in the solvent, the gel is thereby fixed.
  • a defined heat treatment is usually carried out.
  • oxide ceramic layers is generally gone from metal alkoxides, with a 4-valent metal such as silicon, titanium or zirconium or a 3-valent metal such as aluminum, yttrium or boron, the respective alkoxide characterizes.
  • the corresponding metal is bound via oxygen to alkyl groups.
  • thin oxide-ceramic layers such as SiO 2, ZrO 2, TiO 2, Al 2 O 3, which can be sintered, are formed in the manner described.
  • the thickness of such layers is limited to a few 100 nm, since with purely oxide-ceramic layers by the conversion into a gel through the progressive crosslinking, the ductility decreases and subsequently the resulting internal stresses during further crosslinking, for example by shrinkage processes, can no longer be compensated by internal deformations .
  • organic additives which due to their chemical and physical properties only emerge from the gel film at higher temperatures and can ensure the necessary ductility during the heat treatment up to this point. In this way, the internal stresses in the gel can be broken down and cracking prevented.
  • One way to increase the layer thickness, without the risk of cracks provides, to increase the gel ductility organically modified silanes, short ORMOSILe, add to the sol. This results in organic-inorganic hybrid materials which, while retaining the good properties of purely ceramic layers, allow an increase in the layer thicknesses.
  • ZrO 2 ceramic is particularly resistant and hard (1100 HV to 1400 HV) and also chemically very resistant. If particularly large layer thicknesses are to be striven for, organic-inorganic hybrid layers, as mentioned above, are suitable for producing ORMOSILs.
  • TEOS tetraethoxyorthosilane
  • ORMOSIL® network-modifying for example methyltriethoxysilane, MTES
  • network-forming for example methacryloxypropyltrimethoxysil
  • MATMS methacryloxypropyltrimethoxysil
  • the present invention is based on the use of the sol-gel technique described here for the production of tribological layers on hardened steels.
  • the laser is pulsed and that the time relationship between the laser pulses and the dark phases between the laser pulses serves as a control variable for limiting the temperature of the component.
  • the coating is heated sufficiently to achieve sintering and densification, but that because of the high achievable temperature gradient, the underlying component is not yet on the tempering temperature is heated.
  • the layer thickness of the gel is at least equal to the wavelength of the laser.
  • Particularly resistant and suitable for many tribological applications coatings are obtained by a combination of ceramic oxides, titanium, zirconium and silicon.
  • portions of silicon, titanium and zirconium are advantageously selected such that dissolved in the sol between 40 and 50% by weight polysiloxane 1: 1 in octane, between 40 and 50% by weight Al 2 O 3 powder dissolved 1: 1 in nonanol and between 10 and 20% by weight zirconia powder (ZrO2-Y2O3) 1: 1 dissolved in ethanol.
  • Other solvents, in particular a common solvent for all substances are also conceivable.
  • Such a layer adheres particularly well to a steel and on the other hand tough enough to have particularly damping properties, so that such layers are particularly roll over. As a result, they are particularly well suited for rolling bearing applications.
  • At least one further sol-gel layer is applied to the silicon dioxide layer produced in this way and then sintered. This sintering can be carried out, for example, again by means of the mentioned laser process.
  • the invention further relates to a coating in which at least one lacquer-like layer, in particular for example a polyimide layer, is provided above the sintered layers.
  • at least one lacquer-like layer in particular for example a polyimide layer
  • the sintered layers are smoothed, possibly existing pores are closed and possibly dissolved by abrasion particles again bound. It can be used particularly oliophilic substances, whereby the lubricating properties of corresponding rubbing surfaces are improved.
  • the laser sintering is supported by the action of microwave radiation and / or induction.
  • the microwave radiation and the induction effect may also be pulsed. Due to the different penetration depth of laser radiation, induction and microwave radiation, in combination, an even higher temperature gradient can be achieved in the coating material. It can also be increased by the supportive measures of microwave radiation and induction, the temperature initially homogeneous and then additionally pulsed laser light are irradiated to produce temperature peaks.
  • the sol used for the coating is prepared using a metal alcoholate.
  • the metal ion involved can be, for example, silicon, aluminum, beryllium, boron, chromium, titanium, thorium, tungsten, ytterbium or zirconium. It is also possible to use a mixture of the corresponding metal alkoxides.
  • tetraethoxysilane can be used as the metal alkoxide.
  • organically modified silanes for example, 3-aminopropyltruthoxysilane, methyltriethoxysilane, methacryloxipropyltriethoxysilane or methylcellulose can be used.
  • a solid nanocrystalline metal oxide powder of aluminum, beryllium, boron, chromium, silicon, titanium, thorium, tungsten, ytterbium or zirconium may be used, each adapted to the metal ion underlying the metal alkoxide.
  • the invention also relates to a component, in particular a rolling bearing component or a hydraulic support element, at least in the area a mechanically stressed surface made of a hardened steel, with a coating according to one of claims 1 to 15.
  • the invention relates to a method for producing a coating according to any one of claims 1 to 15, wherein a sol-gel is applied to the surface and sintered there by means of a laser and wherein the laser power is controlled such that on the surface of the component the tempering temperature is not exceeded.
  • the sintering preceding transition phase of the sol to a gel, evaporate in the solvent or water and a crosslinking takes place, can advantageously take place with heat application, in particular at temperatures between 0 and 300 ° C.
  • the said transition process can be made particularly advantageous in that it takes place in a protective gas atmosphere, for example from nitrogen, hydrogen or ammonia.
  • Nitrogen and noble gases can also be combined.
  • the components which are provided with the coating according to the invention case hardened or carbonitrided under heat treatment or hardened and tempered.
  • the laser power is then controlled during sintering in such a way that the temperatures of the components to be coated do not exceed 250 ° C. or the individual tempering temperature.
  • DSV thin film method
  • PVD physical vapor deposition
  • PACVD physically cally assisted chemical vapor deposition
  • FIG. 1 shows how a rolling bearing component, symbolized by the ring 1, immersed in a sol 2 within a container 3 and slowly pulled out of this again.
  • the extraction speed can be quite a few centimeters per minute and the movement should be carried out as uniformly as possible when pulling out.
  • the ring 1 consists of a typical bearing steel and is to be provided with an insulating coating in the form of an oxide ceramic.
  • the ring 1 Before coating, the ring 1 is cleaned, for example in a conventional hot degreasing bath with surfactants. It may also be provided a temporary corrosion protection on which adhere to the deposited sol-gel layers.
  • the component to be coated has uniformly curved surfaces in order not to achieve uneven layer thicknesses by the effects of surface tensions.
  • the sol 2 consists either of a true chemical solution of a metal alcoholate or of a colloidal solution, whereby both forms of appearance can also be mixed, in particular if a nanopowder is added to the sol to achieve higher layer thicknesses.
  • organically modified silanes may be added in addition or as an alternative to the nanopowder.
  • rolls or spraying can also be provided as a coating method.
  • TEOS tetraethoxysilane pre-hydrolyzed by the addition of 0.01 N hydrochloric acid
  • the molar ratio of TEOS to water may be for example 1 to 17.
  • the sol thus obtained has a pH of about 2.9 and is stable for a long time (weeks) without observing solidification or flocculation of silica constituents.
  • the condensation can then be catalyzed. This occurs in the basic range by addition of 0.08 NaOH. This initiates the polycondensation and thus the conversion to a gel.
  • acetic acid, glycine or aminocaproic acid or a mixture of these substances are added to the starting sol to prevent the metal alkoxide complex from precipitating. It can thus be stabilized for a long time, so that the sol is easily storable and applicable in industrial applications.
  • the stabilization with acetic acid has been found to be particularly advantageous.
  • the acetic acid causes an acceleration that promotes gelation.
  • the MTS / TEOS brine can also be used in conjunction with organically modified zirconium, whereby the sol is made alkaline. Such sols show excellent coating behavior and can be applied in a relatively large layer thickness without cracking.
  • acid-stabilized colloidal aluminum sols show advantages over base-catalyzed and have particle sizes of about 80 nanometers. Under these conditions, the balance of hydrolysis and condensation is on the side of hydrolysis. At ph values of 2 to 5, however, the condensation determines the reaction rate. Monomers and smaller oligomers with reactive silanol groups are then present side by side. Further condensation leads to a weakly branched network with small cage-like units.
  • the equilibrium is on the side of the condensation, that is, after slow formation of hydrolysates, the condensation reaction begins immediately, forming separate highly crosslinked polysiloxane units.
  • hydrolysis is the rate-limiting factor. The clusters grow by condensation with monomers. This results in crosslinking structures with large particles and pores.
  • sodium hydroxide or ammonia are used in the base-catalyzed sol-gel process. The reaction rate then depends essentially on the base strength, similar to the acid catalysis of the acid strength.
  • the structure of the formed condensates depend on the type of solvent, the type and chain length of the alkoxy function, the molar water / silicon ratio, the substance concentrations, the temperature, the type and concentration of the catalyst, evaporation rates and the amount of water added from.
  • the reactions depend similarly on the water concentration, with a molar ratio of less than 2, the condensation dominates with elimination of alcohol, with ratios greater than 2, the condensation with dehydration.
  • Particularly advantageous for the formation of crack-free layers are molar ratios between 1 to 4 and about 1 to 11 between water and silicon.
  • the gel can be densified in thermal drying, whereby crosslinking also takes place in the gel on the component. This advantageously takes place at temperatures of up to 200 ° C. In so far as ormosils have been used, an organic-inorganic hybrid layer which resembles a conventional lacquer is produced. Further heating or laser application leads to decomposition and removal of organic components, pyrolysis and finally a fusion of the ceramic components with simultaneous collapse of the pores.
  • the component to be coated does not lose its hardness at the required temperatures, the required temperature is only locally very limited generated by the action of a laser, so that the achievable temperature gradients, the temperature drop is sufficiently large to protect the component.
  • the thickness of the gel layer is at least as great as the average roughness depth. Then, the surface roughness is sufficiently covered and a closed layer is formed, which can ensure, for example, the requirement of electrical insulation.
  • a small surface roughness of the component to be coated is advantageous in the coating insofar as the defect density also decreases with decreasing surface roughness. This results in a more uniform join in the coating. Growth defects become rarer.
  • the achievable in the coating gel thicknesses are in pure oxide ceramic coating only a few tenths of a micron. If a nanopowder is additionally dispersed in the sol, layers up to 25 microns thick can be achieved. Otherwise, multilayer coatings having a total thickness of more than one micrometer can also be produced by multiple coating with sol-gel layers and layer-wise laser sintering in each case before application of the next sol-gel layer.
  • the gel coated ring 1 ' is in the middle of the FIG. 1 symbolically represented during the drying and evaporation process.
  • the lower part of the FIG. 1 represents the actual sintering process, wherein the ring is designated 1 "and is irradiated by means of a laser 4.
  • the laser may be a helium-neon laser, a krypton ion laser, a neodymium laser or a Y-AG laser
  • the laser is advantageously pulsed between the nano and millisecond range.
  • the underlying component is only indirectly heated.
  • the shock-like heating by the laser also leads to thermoelastic effects, which excite a broad spectrum of ultrasonic waves. This leads to a further compaction of the sintered layer and to a reduction of the pores. An additional contribution to this is provided by the pulsation.
  • an induction device 5 is shown symbolically and a microwave device 6, both of which additionally or in alternation with the laser 4, continuously or also pulsed, can be operated.
  • FIG. 2 In principle, the layer structure in a finished coated component 1 is shown.
  • the component 1 consists for example of a hardened bearing steel. This is coated with an oxide ceramic layer 7, for example made of silicon dioxide, which is produced by means of laser sintering from a sol-gel. On the first layer 7, a further layer 8 is arranged, which may for example consist of another oxide ceramic substance, zirconium dioxide. The zirconia layer may be further covered with a varnish material such as a polyimide 9 to flatten the surface and bind detached particles as well as close the pores.
  • a varnish material such as a polyimide 9 to flatten the surface and bind detached particles as well as close the pores.
  • the invention makes it possible to produce insulating ceramic or organoanorganic ceramic layers even on steels which have to be protected from excessive temperature increase because of their hardening in a coating method which can be used industrially easily.
  • the process is environmentally friendly and inexpensive and can be flexibly changed and adjusted by adjusting the properties of the sol.

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Claims (16)

  1. Procédé de fabrication d'un composant (1) muni d'un revêtement, le composant (1) comprenant une surface sollicitée mécaniquement et étant constitué d'un acier durci au moins dans la zone de la surface sollicitée mécaniquement, le revêtement étant formé au moins sur la surface sollicitée mécaniquement, au moins une couche sol-gel (7, 8) étant appliquée sur la surface du composant (1), ladite au moins une couche sol-gel (7, 8) étant transformée en un gel et frittée au moyen d'un laser (4), caractérisé en ce que la puissance du laser (4) est ajustée de sorte que la température de revenu de l'acier durci ne soit pas dépassée sur la surface du composant (1).
  2. Procédé selon la revendication 1, caractérisé en ce que le laser (4) est pulsé, un rapport temporel entre les impulsions laser et les phases sombres entre les impulsions laser servant de grandeur de contrôle pour limiter la température du composant (1).
  3. Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce que le rayonnement laser est complété par l'utilisation au moins périodique d'un rayonnement micro-onde ou d'une induction.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'après l'application et le frittage d'une première couche sol-gel (7), une couche sol-gel supplémentaire (8) est appliquée sur la première couche sol-gel (7).
  5. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'après l'application d'une première couche sol-gel (7), celle-ci est tout d'abord gélifiée, puis une couche sol-gel supplémentaire (8) est appliquée et celles-ci sont frittées conjointement sous l'effet d'un laser (4).
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'épaisseur de couche du gel est choisie au moins égale à la longueur d'onde du laser (4) .
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que des colorants qui absorbent le rayonnement laser plus fortement que le gel sont ajoutés au gel.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que pour la formation de la couche sol-gel (7, 8), un sol (2) est utilisé, qui contient entre 40 et 50 % en poids de polysiloxane dissous dans le solvant, entre 40 et 50 % en poids de poudre d'Al2O3 dissoute dans le solvant, et entre 10 et 20 % en poids de poudre d'oxyde de zirconium (ZrO2-Y2O3) dissoute dans le solvant.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'une couche de dioxyde de silicium céramique (7), qui est frittée par un rayonnement laser au moyen du laser (4), est appliquée directement sur l'acier durci.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'une couche de type vernis (9), notamment une couche de polyimide, est prévue sur le revêtement.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'un sol (2) utilisé pour la formation de la couche sol-gel (7, 8) contient au moins un alcoolate métallique.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'un sol (2) utilisé pour la formation de la couche sol-gel (7, 8) contient du TEOS (tétraéthoxysilane).
  13. Procédé selon la revendication 11 ou 12, caractérisé en ce que le sol (2) contient au moins un ORMOSIL (silane modifié organiquement) formant un réseau et/ou modifiant un réseau.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'un sol (2) utilisé pour la formation de la couche sol-gel (7, 8) contient une nanopoudre d'une substance céramique, notamment d'un oxyde métallique.
  15. Procédé selon la revendication 14, caractérisé en ce que la nanopoudre est à base du même ion métallique qui forme la base du sol (2) sous la forme d'un alcoolate métallique.
  16. Composant, qui est constitué d'un matériau durci au moins dans la zone d'une surface sollicitée mécaniquement et qui est muni d'un revêtement, fabriqué selon l'une quelconque des revendications 1 à 15.
EP08717034.6A 2007-03-31 2008-02-22 Revêtement d'un composant en acier trempé et procédé d'application du revêtement Revoked EP2134885B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007015635A DE102007015635A1 (de) 2007-03-31 2007-03-31 Beschichtung eines Bauteils aus gehärtetem Stahl und Verfahren zum Aufbringen der Beschichtung
PCT/EP2008/052170 WO2008119600A1 (fr) 2007-03-31 2008-02-22 Revêtement d'un composant en acier trempé et procédé d'application du revêtement

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EP2134885A1 EP2134885A1 (fr) 2009-12-23
EP2134885B1 true EP2134885B1 (fr) 2018-01-17

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EP08717034.6A Revoked EP2134885B1 (fr) 2007-03-31 2008-02-22 Revêtement d'un composant en acier trempé et procédé d'application du revêtement

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EP (1) EP2134885B1 (fr)
DE (1) DE102007015635A1 (fr)
WO (1) WO2008119600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020116991B3 (de) 2020-06-29 2021-09-02 Franz Durst Atemluftfilter und Verfahren zum Betrieb eines Atemluftfilters

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2715958A1 (fr) * 2009-10-12 2011-04-12 General Electric Company Procede de realisation de preparation de revetement, preparation de revetement resultante, et revetement des elements connexe
DE102011077023A1 (de) * 2011-06-07 2012-12-13 Schaeffler Technologies AG & Co. KG Beschichtungsverfahren und Beschichtung für ein Lagerbauteil
EP2987776A1 (fr) 2014-08-21 2016-02-24 4JET Technologies GmbH Traitement thermique d'une couche de silicate avec un laser au dioxyde de carbone pulsé
DE102016115746A1 (de) * 2016-08-24 2018-03-01 Dechema-Forschungsinstitut Mehrschichtiges Zunderschutzsystem für presshärtbare Stähle
CN114622190A (zh) * 2022-02-28 2022-06-14 武汉理工大学 一种一步化凝胶溶胶提拉烧结镀膜装置及其使用方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999044822A1 (fr) 1998-03-05 1999-09-10 Koninklijke Philips Electronics N.V. Procede permettant d'appliquer une couche de ceramique sur une sous-couche possedant une temperature de fusion relativement basse
EP1176228A2 (fr) 2000-07-26 2002-01-30 DaimlerChrysler AG Couche superficielle et son procédé de fabrication
DE102004052135A1 (de) 2004-06-07 2005-12-29 Fachhochschule Schmalkalden Beschichtetes Metallsubstrat und Verfahren zu seiner Herstellung

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087250B (en) * 1977-11-01 1982-12-08 Atomic Energy Authority Uk Catalyst preparation
DE59108716D1 (de) 1990-04-27 1997-07-03 Saphirwerk Ind Prod Wälzkörper, Verfahren zu seiner Herstellung und Wälzkörper- oder Gleitlager
JP2991834B2 (ja) 1991-10-14 1999-12-20 正二郎 三宅 転がり軸受
US5585136A (en) * 1995-03-22 1996-12-17 Queen's University At Kingston Method for producing thick ceramic films by a sol gel coating process
NL1007046C2 (nl) 1997-09-16 1999-03-17 Skf Ind Trading & Dev Bekleed wentellager.
NL1019860C2 (nl) 2002-01-30 2003-08-05 Skf Ab Wentellager met een keramisch wentelelement en stalen binnen- of buitenring.
DE102005017088A1 (de) * 2005-04-13 2006-10-19 Stiftung Institut für Werkstofftechnik Schutzschichten

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999044822A1 (fr) 1998-03-05 1999-09-10 Koninklijke Philips Electronics N.V. Procede permettant d'appliquer une couche de ceramique sur une sous-couche possedant une temperature de fusion relativement basse
EP1176228A2 (fr) 2000-07-26 2002-01-30 DaimlerChrysler AG Couche superficielle et son procédé de fabrication
DE102004052135A1 (de) 2004-06-07 2005-12-29 Fachhochschule Schmalkalden Beschichtetes Metallsubstrat und Verfahren zu seiner Herstellung

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Sol-Gel-Prozess, Wikipedia", 10 March 2007 (2007-03-10), pages 1pp, XP055525798, Retrieved from the Internet <URL:https://de.wikipedia.org/w/index.php?title=Sol-Gel-Prozess&oldid=28964399>
CHUNG J., KO S., GRIGOROPOULOS C.P. ET AL.,: "Damage-Free Low Temperature Pulsed Laser Printing Of Gold Nanoinks On Polymers", JOURNAL OF HEAT TRANSFER - TRANSACTIONS OF THE ASME, vol. 127, July 2005 (2005-07-01), pages 724 - 732, XP055525782
EZZ T; CROUSE P; LI L; LIU Z: "Laser /sol-gel synthesis: a novel method for depositing nanostructured TiN coatings in non-vacuum conditions", APPLIED PHYSICS A - MATERIALS SCIENCE & PROCESSING, vol. 85, no. 1, 29 July 2006 (2006-07-29), pages 79 - 82, XP019424437
H. K. SCHMIDT: "Anorganische Synthesemethoden Das Sol-Gel-Verfahren", CHEMIE IN UNSERER ZEIT, vol. 35, no. 3, 2001, pages 176 - 184, XP055525804, ISSN: 0009-2851
JEFF T.M. DE HOSSON, R. POPMA: "Sintering characteristics of nano-ceramic coatings", DEFECT AND DIFFUSION FORUM, vol. 218-220, 8 August 2003 (2003-08-08), pages 51 - 66, XP055525793, ISSN: 1662-9507

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020116991B3 (de) 2020-06-29 2021-09-02 Franz Durst Atemluftfilter und Verfahren zum Betrieb eines Atemluftfilters
EP3932517A1 (fr) 2020-06-29 2022-01-05 Franz Durst Filtre d'air aspiré et procédé de fonctionnement d'un filtre d'air aspiré

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WO2008119600A1 (fr) 2008-10-09
DE102007015635A1 (de) 2008-10-02

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