EP3084048B1 - Procédé pour produire une couche protectrice sur un composant soumis à des contraintes thermiques, et composant doté d'une couche protectrice de ce type - Google Patents

Procédé pour produire une couche protectrice sur un composant soumis à des contraintes thermiques, et composant doté d'une couche protectrice de ce type Download PDF

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Publication number
EP3084048B1
EP3084048B1 EP14851435.9A EP14851435A EP3084048B1 EP 3084048 B1 EP3084048 B1 EP 3084048B1 EP 14851435 A EP14851435 A EP 14851435A EP 3084048 B1 EP3084048 B1 EP 3084048B1
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EP
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Prior art keywords
protective layer
component
particles
set forth
thermal conductivity
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EP14851435.9A
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German (de)
English (en)
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EP3084048A1 (fr
Inventor
Alexander Kopp
Christoph PTOCK
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Volkswagen AG
Meotec GmbH and Co KG
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Volkswagen AG
Meotec GmbH and Co KG
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Priority claimed from DE102014219819.4A external-priority patent/DE102014219819A1/de
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Publication of EP3084048A1 publication Critical patent/EP3084048A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/14—Tubes; Rings; Hollow bodies
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the present invention relates to a method for producing a protective layer on a thermally stressed component and to a component having such a protective layer.
  • the present invention relates to an electrochemical process for producing an oxidation, wear or corrosion protection layer on a component of an internal combustion engine or a component of an exhaust system.
  • Such components are used in particular in motor vehicles.
  • motor vehicles there is an effort to reduce the total weight of the vehicle and therefore its individual components, so as to increase the efficiency. It therefore makes sense to resort to particularly lightweight materials, in particular so-called light metals such as aluminum, titanium, or their alloys.
  • a problem or disadvantage of these materials is the relatively good thermal conductivity, so that the use of these materials, especially for components that are exposed to higher temperatures, for example, about 300 ° C, not readily possible.
  • Due to the system such high temperatures occur in motor vehicles in the internal combustion engine and in the exhaust system.
  • an exhaust gas turbocharger may be mentioned, in which temperatures of over 900 ° C may occur. At such temperatures, so-called hot gas corrosion may occur due to the particularly hot gas (the hot gas).
  • the surface In order to enable the use of such materials even with thermally stressed components, the surface must be provided with a protective layer, by which in particular the heat conduction coefficient is reduced.
  • spraying processes for example thermal spraying or plasma spraying
  • a disadvantage of this solution is that in such spray coatings the connection between the sprayed protective layer and the component is achieved by a mechanical clamping of the layer material (eg by flakes) on the substrate, ie the surface of the component, or by adhesion processes or diffusion processes. In operation, it can therefore cause problems due to spalling or due to a lack of abrasion resistance.
  • the known spray methods are expensive and energy consuming.
  • an oxide layer has recently been proposed as a protective layer. That's how it shows DE 10 2012 002 284 A1
  • a turbine wheel on or in the surface of a halide from the group corridor, chlorine or bromine or is introduced and on the surface of an oxidation layer is formed by the so-called halogen effect in a heat treatment.
  • the halogens are applied in particular by ion implantation.
  • a disadvantage of such methods for producing a protective layer on a thermally stressed component based on the halogen effect is that the oxide layers formed are very thin. Thus, there is only a limited improvement in corrosion resistance, so that the wear protection is not optimal. Furthermore, owing to the relatively thin oxide layer, no major influence on the electrical or thermal insulation of the component is to be expected.
  • an oxide layer by electrochemical methods is proposed. From the DE 10 2012 218 666 A1 is such a method known.
  • a turbine wheel of a titanium alloy turbocharger is subjected to electrochemical anodization, which constructs an oxide film as a protective layer and thus protects the component from further oxidation. Furthermore, the component is thus protected against further environmental influences.
  • EP 2 371 996 A1 discloses a method of electrolytic ceramic coating on metal, wherein at least one metal is used as an anode to perform anodization treatment of an anode surface in a given electrolytic solution for ceramic coating by generating glow discharge and / or arc discharge, thereby forming a ceramic coating on the metal surface wherein the average current density during the application of the positive side is in the range of 0.5 A / dm 2 to 40 A / dm 2 , and wherein the anodization treatment at a positive side operating time ratio (T1) of 0.02 to 0.5, an operating time ratio of the negative side (T2) of 0 to 0.5, a non-application time ratio (T3) of 0.35 to 0.95 and wherein these ratios simultaneously satisfy the following formulas: 0 ⁇ T2 / T1 ⁇ 10 and 0.5 ⁇ T3 / (T1 + T2) ⁇ 20.
  • T1 positive side operating time ratio
  • T2 operating time ratio of the negative side
  • T3 non-application time
  • the EP 2 103 718 A1 discloses another method of applying a ceramic film to a metal which can form a dense metal-based film such as magnesium alloys.
  • the formed ceramic film has excellent abrasion resistance, hardly attacks a corresponding material, and moreover has an excellent abrasion performance.
  • the CA 2 479 032 A1 discloses a coating consisting of an oxide / lubricant composite coating on light alloys based on plasma oxidation in conjunction with solid lubricant agents which are rubbed against an oxide surface during coating formation.
  • EP 2 721 270 A1 there is disclosed a method of reducing emissions and / or reducing friction in an internal combustion engine, wherein a portion of the combustion chamber of aluminum and / or titanium is coated with titanium oxide, further comprising dopants in and / or on the adhered titanium oxide coating.
  • the resulting zirconium coating consists of tetragonal zirconia of monoclinic zirconia and of gamma-type alumina.
  • the thickness of the coating is 20 ⁇ m to 300 ⁇ m.
  • the coating is suitable for complex structures and has a strong bond with the carrier. Furthermore, it is characterized by a high hardness of 1700 HV to 1800 HV.
  • the object of the present invention to provide an inexpensive method for producing a protective layer on a thermally stressed component, which allows the application of a protective layer even on hard to reach surfaces, has a good adhesion to the surface and thus an optimal oxidation , Wear and corrosion protection offers.
  • local temperature maxima are to be reduced in a combustion chamber, which is to be thermally insulated at the same time.
  • a method for producing a protective layer on a thermally loaded component which consists at least partially of a valve metal, wherein the protective layer is produced by an electrochemical process.
  • the method according to the invention is characterized in that the electrochemical process is a plasma electrolytic oxidation (PEO) using an electrolyte and applying an electrical power.
  • the method is characterized in that particles are deposited in the protective layer, which relative to a base material of the protective layer, a relative have low or high thermal conductivity, wherein the particles are provided with relatively high thermal conductivity in a first sub-layer of the protective layer and the particles with relatively low thermal conductivity in a second, separated by the first sub-layer sub-layer.
  • a valve metal is here understood to mean a metal in which the surface can be converted by an electrochemical process into an oxide ceramic layer or an oxide layer, such as titanium (Ti), aluminum (Al), magnesium (Mg) or zirconium (Zr) or their alloys.
  • the surface reacts by applying an electrical power in a local plasma via spark discharge and forms an oxide ceramic or layer.
  • the electrolyte-exposed surface is "scanned”, governs electrochemically with the cleaved oxygen and / or the electrolyte to an oxide ceramic or layer (for example, Al 2 O 3 , spinels, mixed oxides, etc.).
  • a PEO process is an anodic oxidation process using a specially modulated AC voltage, resulting in a temporary and localized spark discharge due to plasma discharges.
  • the PEO process is therefore also referred to as anodic oxidation with spark discharge (ANOF).
  • ANOF anodic oxidation with spark discharge
  • An ANOF process or a PEO process according to the invention is a combined process from the fields of plasma technology and electrochemistry, by means of which surfaces of components which are formed of so-called valve metals can be provided with a protective layer of an oxide ceramic.
  • native barrier layer formers such as aluminum, magnesium or titanium come into the selection as valve metals.
  • the generation of the protective layer can in particular take place in aqueous electrolytes.
  • the component to be oxidized is poled anodically and immersed in the electrolyte together with a counter electrode (cathode).
  • the component initially forms a purely chemically induced passive layer. The growth of this passive layer can be achieved by applying a potential between the anodically poled component and the cathode.
  • the oxide layer of the component to be coated will penetrate locally, wherein plasma-chemical solid-state reactions, the spark discharges, are triggered.
  • This process does not take place nationwide but at those points where the thickness of the oxide layer and thus the local electrical resistance is lowest. Since the plasma reactions thus always take place at those points of the passive layer which locally have the lowest layer thickness, and there ensure a layer thickness growth, the surface is coated with a very uniform protective layer.
  • the applied electric potential is increased so long that the desired layer thickness of the protective layer is reached.
  • the inventive method has the advantage that the layer formed has a defined thermal conductivity according to their ceramic character, which is well below the thermal conductivity of the substrate material, for example aluminum. Due to the smaller planteleitkoe slaughteren and the low thermal conductivity of the protective layer thus higher wall temperatures are possible, so that the surface provided with the protective layer against the adjacent medium, such as hot gas, is thermally insulated.
  • the protective layer produced by the method according to the invention is therefore constructed as follows: Adjacent to the substrate is a thin, dense and closed layer, the so-called barrier layer, followed by a compact and low-pore layer. This is followed by a porous and less compact layer which, depending on the layer thickness, becomes both more porous and more brittle.
  • this layer is openly porous and characterized by small channels which are perpendicular to the surface and protrude from the surface to the adjacent barrier layer in the direction of the substrate.
  • the layer has an interconnecting pore network and / or a non-interconnecting pore network, which is characterized by closed inclusions of air or electrolyte.
  • the electrolyte has an electrolyte base, wherein the electrolyte base is phosphoric acid (H 3 PO 4 ), potassium hydroxide (KOH), water glass (Na 2 SiO 3 ), deionized water or a zirconium-containing compound.
  • An electrolyte base here is a substance from a variety of substances, the amount (in g / L) in addition to water and urotropin is most common in an electrolyte.
  • Zirconium sulfate (ZrSO 4 ) or zirconium tungstate (ZrWO 4 ) is particularly suitable as the zirconium-containing compound. This has the advantage that with such an electrolyte composition, a component of, for example, aluminum or titanium or of the corresponding alloys can be plasma-electrochemically oxidized at all.
  • the electrical power is voltage controlled, the current is limited, or is current-controlled, the voltage is limited, or is power-controlled.
  • the electrical power is applied at a frequency of 1 Hz to 10 kHz, in particular with a frequency of 1 Hz to 1000 Hz.
  • the voltage is applied in a range between 150 volts and 1500 volts, preferably in a range between 210 volts and 650 volts, and if the current has a current density in a range between 0.001 A / dm 2 and 1000 A / dm 2 , preferably in a range between 0.5 A / dm 2 to 15 A / dm 2 is applied.
  • the applied current and / or the applied voltage is supermodulated by a higher-frequency current and / or a higher-frequency voltage. Furthermore, it is advantageous if the applied current and / or the applied voltage is rectified or has the form of a symmetrical wave, an asymmetric wave, a rectangle or a trapezoid.
  • the shape of a wave is advantageous.
  • a temperature in the range between 0 ° C and 80 ° C is selected as the process temperature for the PEO. More preferably, the temperature is between 18 ° C and 50 ° C.
  • the abovementioned process parameters make it possible for a particularly oxide-rich protective layer to grow closed on the component and thus to form a particularly dense and therefore safe protective layer.
  • the component can be protected so safe and long-term stability against external influences, for example, from undesirable oxidation.
  • components can be produced in mass production with corresponding quality requirements. Furthermore, a practicable production speed can be achieved in this way, which makes mass production possible at all.
  • the electrolyte is carried out as a dispersion, wherein one or more of the following particles are added to the electrolyte: Al 2 O 3 , TiO 2 , SiO 2 , tungsten carbide (WC), ZrO 2 , iron oxide, graphite and / or MoS 2 .
  • the electrolyte is subjected to an electrolyte base by the addition of said particles.
  • the particles can be either globular, ellipsoidal or sparse, in the form of flakes or the like.
  • the particles can be made of an oxide, a carbide or another material, as long as the particles are incorporated as a foreign body into the protective layer or react chemically, electrochemically or physically with the substrate or the electrolyte to form a different compound.
  • particles of Al 2 O 3 , TiO 2 , SiO 2 , tungsten carbide (WC), ZrO 2 , iron oxide have a significantly reduced thermal conductivity, so that the incorporation of these particles in the protective layer further improves the insulating effect of the protective layer.
  • zirconium oxide (ZrO 2 ) has proved to be advantageous.
  • lubricant particles such as graphite, MoS 2 or other corresponding particles which are incorporated into the protective layer, the coefficient of friction is reduced.
  • particles are provided in the protective layer of a material deviating from a base or matrix material of the protective layer, which have a relatively high or low thermal conductivity compared to the base or matrix material of the protective layer. Specifically, both those particles are provided which have a relatively high thermal conductivity compared to the base or matrix material of the protective layer, as well as those which have a relatively low thermal conductivity.
  • This aspect of the invention is based, on the one hand, on the recognition that the protective layer produced in the context of the method according to the invention represents an advantageous compromise with regard in particular to thermal insulation and durability, but alternative materials are present which are characterized by an even lower thermal conductivity and thus a lower thermal conductivity further distinguished improved thermal insulation.
  • these can not be used for the complete formation of a protective layer.
  • By introducing particles of one or more of these alternative materials into the protective layer produced according to the invention their average thermal conductivity can be further lowered and thus the thermal insulating properties can be further improved without this to a relevant extent on the further advantageous properties of the protective layer according to the invention, ie especially good durability and low surface roughness, has a negative impact.
  • Y-stabilized zirconia Zr (Y) O 2
  • alumina Al 2 O 3
  • spinel Al 2 O 3 / MgO
  • mullite Al 2 O 3 / SiO 2
  • zirconium corundum Al 2 O 3 / ZrO 2
  • titanium oxide TiO 2
  • silicon oxide SiO 2
  • the thermal conductivity of the introduced particles in their pure bulk state is not lower than that of the matrix
  • the thermal conductivity of the composite material of the protective layer formed from both can nevertheless be lower overall since the particles introduced act as impurities for the propagation of the crystal oscillations (phonons).
  • the concretization "with relatively low thermal conductivity" according to the invention is not limited exclusively to an actual material property of the particles, but should also include a heat conductivity reducing effect within the matrix.
  • the particles with a relatively high thermal conductivity can advantageously be used to avoid or reduce localized peaks of the wall temperature of the surface provided with the protective layer, as a result of these particles being able to achieve a relatively high local transition of heat energy from, for example, a combustion chamber or an exhaust gas guide as well as possible a larger area of the protective layer is distributed.
  • the formation of locally high wall temperatures which can have a negative effect on the ignition delay (ie the period between the injection of fuel into the combustion chamber and the ignition of the fuel), can be avoided.
  • This may be sufficient if the particles with relatively high thermal conductivity in only one or more sections, but not in the entire protective layer (based on the area and preferably also the layer thickness) are provided.
  • Such a localized provision of particles with relatively high thermal conductivity does not therefore have to be associated with a relevant deterioration in the mean thermal conductivity of the entire protective layer.
  • a relatively large ignition delay, achieved by avoiding locally high wall temperatures, is particularly important for self-igniting internal combustion engines, i. diesel engines, in particular, so that the method according to the invention can be used particularly advantageously in the improvement of such a self-igniting internal combustion engine.
  • the method according to the invention can be used particularly advantageously in the improvement of such a self-igniting internal combustion engine.
  • the particles having a relatively high thermal conductivity for example, copper, iron, beryllium, aluminum, copper, silver, silicon, molybdenum, tungsten, carbon, beryllium, beryllium nitrite, silicon nitrite and / or silicon carbide and mixtures and / or alloys thereof come into consideration.
  • both particles with relatively low thermal conductivity and particles with relatively high thermal conductivity are provided.
  • Their distribution in the protective layer should be provided in such a way that the mean thermal conductivity of the protective layer, which is locally increased by the particles having a relatively high thermal conductivity, does not lead to a significantly higher heat transfer to the region of the coated, the combustion chamber and / or the exhaust gas guide-limiting component arranged below the protective layer leads.
  • This is achieved in an advantageous manner in that the particles with relatively high thermal conductivity exclusively in a first, adjacent to the combustion chamber and / or the exhaust gas guide sub-layer of the protective layer and the particles with relatively low thermal conductivity in a second, from the combustion chamber and / or the Exhaust system can be provided by the first sub-layer separate sub-layer.
  • the particles with a relatively high thermal conductivity can then ensure the most uniform possible distribution of heat energy transferred into the protective layer within the first sub-layer, while the second sub-layer with the particles having relatively low thermal conductivity has a particularly good thermal insulating effect and consequently a heat transfer from the first sub-layer reduced lying below the protective layer region of the component.
  • Anodic oxidation under spark discharge makes it possible to arrange particles in the protective layer in a relatively simple manner. This is especially true in the case of an anodic oxidation with spark discharge by means of an alternating voltage, in which either the positive or negative voltage phases can be alternately used to attach the particles contained in the electrolyte to the growing protective layer, while the corresponding other voltage phases for the growing training the protective layer can be used.
  • the particle size of the particles can be in the range from 0.001 ⁇ m to 5000 ⁇ m, in particular in a range between 0.1 ⁇ m to 100 ⁇ m. Such particle sizes have proven to be practicable.
  • an ultrasonic vibrator can be used for uniform dispersion of the particles.
  • the dispersion of the particles in the electrolyte can be done inexpensively and quickly.
  • the particles can be polarized by the use or addition of surfactants.
  • the surfactants may be neutral, positive or especially cationic surfactants (e.g., ester squares) such that the polarized particles are e.g. in the cathodic part of a half-wave are pulled to the surface and in the anodic part of a half wave - in the context of the spark discharge - are integrated into the surface.
  • the object is also achieved by a component with a protective layer, which was produced by the method according to the invention.
  • the component consists at least partially of a valve metal or an alloy of a valve metal.
  • the component is made of aluminum, an aluminum alloy, magnesium, a magnesium alloy, titanium or a titanium alloy.
  • the layer thickness of the protective layer is in a range between 1 .mu.m and 1500 .mu.m.
  • the layer thickness is preferably in a range between 25 ⁇ m and 600 ⁇ m.
  • the component may be a combustion chamber, an engine block, a crankcase, a crankcase interior, a cylinder liner, a cylinder head, an intake manifold, an exhaust manifold, a turbocharger compressor wheel, a turbocharger interior, an exhaust gas recirculation or a cylinder piston.
  • the component is thus thermally less stressed, on the other hand, the temperature of the medium (for example of the hot gas) can thus be maintained over a longer path and time. Furthermore, this leads to the fact that certain aggregates of the automobile respond faster, and also the stored in the gas thermal energy can not be purely thermally dissipated but can be recovered by other aggregates or components.
  • the medium for example of the hot gas
  • the protective layers produced by the process according to the invention have a good resistance to wear, oxidation, erosion and corrosion, which is required in a number of components. Furthermore, as the life of the components is improved. This particularly affects the cylinder bore (tribological wear due to solid, transitional, mixed and / or sliding friction), the compressor wheel of the turbocharger (erosion wear) or the manifold (corrosion resistance).
  • a further advantage of the method according to the invention lies in the applicability and ability to selectively and nevertheless homogeneous coating in cavities, channels or complex geometries with undercuts.
  • a homogeneous protective layer is formed everywhere on the surface where the electrolyte wets the component surface. So undercuts or depressions or channels can be provided with a protective layer.
  • the surface is converted by reaction of the electrolyte with the substrate. That is, there will be no locally dependent on the prevailing field lines material deposition according to the local distribution of the current density, which would be necessary, for example, in complex geometries and undercuts the use of auxiliary electrodes, but it will generate local sparking anywhere where the process-related potential is applied.
  • a protective layer can be produced selectively by means of PEO on the surface sections to be thermally insulated.
  • a concept 1 in the form of an electrolytic cell for the production of a protective layer in a component 2 is shown.
  • the component 2 may for example be a manifold. It is therefore the application of a method shown, in which not the entire component 2 is immersed in the electrolyte for the application of PEO, but the electrolyte is flushed through lying in the interior of the component 2 channels, so that on the inside of the channels of the component 2 selectively generates a suitable protective layer.
  • the interior of the component 2 is sealed with two flanges 3, each having a seal.
  • the electrolyte is pumped through a line assembly 6 through the component 2. In this cycle, the electrolyte is cooled or tempered by the electrolytic cooling 5.
  • the concept 1 has a power supply 7 as a power source, which, as shown, may be a DC power supply or an AC power supply.
  • the component 2 and a counter electrode 9 is connected. Via the flanges 3 and the counter electrode 9 is introduced into the space to be coated in the interior of the component 2.
  • the counter electrode 9 is the cathode, the component 2 representing the anode 10.
  • Fig. 2 a second embodiment is shown.
  • Fig. 2 is made in two parts, with in Fig. 2 Part 1, the plant 1 for producing a protective layer on a component 2, in this example, a cylinder piston head, is shown, and in Fig. 2 Part 2 of the procedural part of the plant with respect to the electrolyte.
  • a component 2 in this example, a cylinder piston head
  • the cylinder piston head 2 in the system 1 is charged with an electrolyte, which is fed by a pump 4 through an inlet valve 11.
  • the circulation of the electrolyte is done via a discharge 12, for example via an extraction, wherein the suction pipe shown is made of a stainless steel, for example made of V2A.
  • the system 1 has a cooling system 13 for the cylinder piston head 2.
  • the power supply 7 is designed such that the discharge 12 simultaneously the counter electrode 9 and the cylinder piston head 2, the anode 10.
  • the in the Fig. 3 shown internal combustion engine includes an example operating on the diesel principle internal combustion engine 110, which is formed for example as a four-cylinder reciprocating internal combustion engine.
  • the internal combustion engine 110 is supplied with fresh gas (ambient air) via a fresh gas train 112.
  • fresh gas ambient air
  • the fresh gas is compressed after being aspirated from the environment by means of a compressor 114.
  • the compressed fresh gas is then passed through a charge air cooler 116, in which the fresh gas heated as a result of the compression is cooled until it reaches the desired temperature for entry into the internal combustion engine 110.
  • a suction pipe 118 the fresh gas enters into combustion chambers 120 of the internal combustion engine 110, in which this or the oxygen contained therein is burned in a known manner with directly injected into the combustion chambers 120 fuel.
  • Exhaust line 122 includes an exhaust manifold 124 in which the exhaust gas flowing out of the individual combustion chambers 120 is brought together, and a turbine 126 arranged downstream thereof.
  • Turbine 126 forms an exhaust gas turbocharger together with compressor 114 and is controlled by means of an adjustable bypass 128 (wastegate ) executed passable.
  • the bypass 128 serves, in certain operating states of the internal combustion engine 110 leading to a large exhaust gas mass flow, to pass part of the exhaust gas mass flow past the turbine 126 in order to limit the charge pressure in the fresh gas train 112.
  • an exhaust aftertreatment device is further integrated.
  • the exhaust aftertreatment devices may include, for example, an oxidation catalyst 130 and a particulate filter 132.
  • the Fig. 4 shows a cross section through the internal combustion engine 110 in the region of a cylinder.
  • the engine 110 includes a cylinder housing 134 that forms the individual cylinders. In each of the cylinders, a piston 136 is guided movable up and down. Above the cylinder housing 134, a cylinder head 138 connects.
  • the cylinder housing 134, the cylinder head 138, and the pistons 136 are formed of aluminum alloys.
  • the intake ports 140 are part of the fresh gas train 112 of the internal combustion engine and connect the suction pipe 118 fluid-conductively with the respective cylinders.
  • the exhaust ports 142 are part of the exhaust line 122 and connect the respective cylinders to the exhaust manifold 124. Via gas exchange valves 144, introduction of the fresh gas into the cylinders and exhaust of the exhaust from the cylinders are controlled in a known manner. In this case, the gas exchange valves 144 are actuated, for example, by means of one or more (not shown) camshafts.
  • the combustion chambers 120 formed by the individual cylinders are each bounded by a portion of the inner wall of the associated cylinder, by the top of the associated piston 136, a portion of the underside of the cylinder head 138, and by the bottoms of the associated gas exchange valves 144.
  • a protective layer 146 is applied by means of anodic oxidation with spark discharge, in particular on the surfaces formed by the upper sides (of main bodies) of the pistons 136.
  • This protective layer 146 consists essentially of aluminum oxide (Al 2 O 3), which forms as part of the anodic oxidation under spark discharge at the tops of the piston 136.
  • the protective layer 146 which may have a layer thickness of, for example, about 200 microns, already characterized in principle due to their training of alumina by a high wear resistance and good thermal resistance, whereby their use to limit the combustion chambers 120 of the engine 110 is possible , Furthermore, the protective layer 146 is characterized by a relatively low thermal conductivity and a relatively low heat capacity compared to the aluminum alloy, from which the piston 136 are formed. This achieves the desired thermal insulation of the combustion chambers and consequently a relatively low heat transfer of gases in the combustion chambers 120 to the pistons 136.
  • the base body of the pistons 136 In order to further reduce a heat transfer from the combustion chambers to the base body of the pistons 136, it is provided to embed particles 148 of, for example, zirconium oxide, which have an even lower thermal conductivity compared to the aluminum oxide. As is clear from the Fig. 5 is provided to provide the particles 148 of zirconia over the entire surface of the protective layer 146 in a (second) sub-layer extending between the surface of the body of the corresponding Piston 136 and another, adjacent to the combustion chamber 120 (first) sub-layer is arranged.
  • the particles 150 of a material for example copper, which is characterized by a relatively high thermal conductivity compared to the matrix material serving as alumina. It is envisaged to provide the particles 150 of copper in those regions of the first sub-layer of the protective layer 146 in which experience has shown that relatively high local wall temperatures may result during the operation of such an internal combustion engine.
  • the particles 150 of copper serve to reduce such locally high wall temperatures by forwarding the increased introduction of heat energy at these points as well as possible to the entire second partial layer.
  • the particles 150 of copper can be arranged, for example, at the edge transitions of a piston recess 152 and in the region of a central elevation of the piston recess 152.
  • the Fig. 5 also shows that also the density of the distribution of the particles 150 of copper, ie the number of particles per unit volume; in the formation of the protective layer 146 by means of anodic oxidation under spark discharge can be controlled (also possible for the particles 148 of zirconia). It is thus provided that in those sections of the first partial layer in which particles 150 of copper are provided, in each case a higher density of particles 150 in a central region and to the edge of the respective section decreasing density of particles 150 provide.
  • the subdivision of the protective layer 146 into the first sublayer and the second sublayer results merely from the different embedding of the different particles 148, 150 and from the different functionalities for the protective layer 146 achieved thereby.
  • a structural parting plane is not formed between the two sublayers.
  • the particles 148, 150 may, for example, have a size of .ltoreq.5 .mu.m.
  • a corresponding protective layer 146 in order to further improve the thermal insulation of the combustion chambers 120.
  • the Fig. 4 shows by way of example that both the inner walls of the cylinders (at least in those sections which delimit the combustion chambers 120), the corresponding portions of the underside of the cylinder head 138 and the lower sides of the gas exchange valves 144, each having a protective layer 146 which was formed by spark discharge anodization , can be coated.
  • FIG. 4 shows the possibility of providing the outlet ducts 142 of the internal combustion engine 110 serving as exhaust gas ducts with corresponding protective layers 146.
  • other surfaces of the exhaust tract 122 of the internal combustion engine serving for exhaust gas routing for example walls of an exhaust manifold and / or a turbine of an exhaust gas turbocharger, can be provided with corresponding protective layers 146.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (15)

  1. Procédé de réalisation d'une couche de protection (146) sur un composant (2) soumis à des contraintes thermiques, qui consiste au moins partiellement en un métal, la surface pouvant être transformée, par un processus électrochimique, en une couche de céramique d'oxyde ou en une couche d'oxyde, sachant que la couche de protection (146) est réalisée par un processus électrochimique et sachant que le processus électrochimique est une oxydation par plasma électrolytique, avec utilisation d'un électrolyte et application d'une puissance électrique,
    caractérisé en ce que, dans la couche de protection (146), sont déposées des particules (148, 150), qui, en comparaison avec le matériau de base de la couche de protection (146), sont dotées d'une conductivité thermique relativement faible ou élevée, sachant que les particules (150) à conductivité thermique relativement élevée sont prévues dans une première couche partielle de la couche de protection (146) et que les particules (148) à conductivité relativement faible sont prévues dans une deuxième couche partielle, sachant que la première couche partielle est séparée du composant (2) par la deuxième couche partielle.
  2. Procédé selon la revendication 1,
    caractérisé en ce que l'électrolyte a un composant électrolytique, sachant que le composant électrolytique est de l'acide phosphorique, de l'hydroxyde de potassium, du verre soluble, de l'eau désionisée ou une composition contenant du zirconium.
  3. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que la puissance électrique est régulée au niveau de la tension, sachant que la puissance du courant est limitée ou régulée au niveau du courant, sachant que la tension est limitée ou régulée au niveau de la puissance.
  4. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que la puissance électrique est appliquée avec une fréquence de 1 Hz à 10 kHz, en particulier avec une fréquence de 1 Hz à 1000 Hz.
  5. Procédé selon l'une des revendications 3 ou 4,
    caractérisé en ce que la tension appliquée est située dans une gamme de 150 Volt à 1500 Volt, de préférence dans une gamme de 210 Volt à 650 Volt.
  6. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que l'électrolyte est effectué en tant que dispersion, sachant que l'une ou plusieurs des particules (148, 150) suivantes sont ajoutées à l'électrolyte ;
    Al2O3, TiO2, SiO2, WC, ZrO2, oxyde de fer, graphite et / ou MoS2.
  7. Procédé selon l'une des revendications 1 à 6,
    caractérisé en ce que les particules (148) à conductivité thermique relativement faible sont prévues sur toute la surface de la couche de protection (146) dans la deuxième couche partielle.
  8. Procédé selon l'une des revendications 1 à 7,
    caractérisé en ce que les particules (150) à conductivité thermique relativement élevée ne sont prévues que dans une ou plusieurs sections de la première couche partielle (146).
  9. Procédé selon l'une des revendications 1 à 8
    caractérisé en ce que, pour les particules (150) à conductivité thermique relativement élevée, on utilise du cuivre, du fer, du béryllium, de l'aluminium, de l'argent, du silicium, du molybdène, du wolfram, du carbone, de l'oxyde de béryllium, du nitrite de béryllium, du nitrite de silicium et / ou du carbure de silicium, ainsi que des mélanges et / ou des alliages de ceux-ci.
  10. Composant (2) avec une couche de protection (146), sachant que la couche de protection (146) a été réalisée par un procédé selon l'une des revendications 1 à 9, sachant que le composant (2) consiste au moins partiellement en un métal, la surface pouvant être transformée, par un processus électrochimique, en une couche de céramique d'oxyde ou en une couche d'oxyde, et que, dans la couche de protection (146), sont déposées des particules (148, 150), qui, en comparaison avec le matériau de base de la couche de protection (146), sont dotées d'une conductivité thermique relativement faible ou élevée, sachant que les particules (150) à conductivité thermique relativement élevée sont prévues dans une première couche partielle de la couche de protection (146) et que les particules (148) à conductivité relativement faible sont prévues dans une deuxième couche partielle, sachant que la première couche partielle est séparée du composant (2) par la deuxième couche partielle..
  11. Composant (2) selon la revendication 10,
    caractérisé en ce que le composant (2) est fabriqué en aluminium, en alliage d'aluminium, en magnésium, en alliage de magnésium, en titane ou en alliage de titane.
  12. Composant (2) selon revendication 10 ou 11,
    caractérisé en ce que la couche de protection (146) présente une épaisseur de couche qui est située entre 1 µm et 1500 µm, de préférence entre 25 µm et 600 µm.
  13. Composant (2) selon l'une des revendications 10 à 12,
    caractérisé en ce que le composant (2) est un bloc de moteur, un carter de vilebrequin, une tête de cylindre (138), un collecteur d'admission, un collecteur d'échappement (124), une roue de turbocompresseur, une chambres interne d'un turbocompresseur, un retour de gaz d'échappement ou un piston de cylindre (136).
  14. Machine à combustion avec un composant (2) selon la revendication 13.
  15. Véhicule automobile avec un composant (2) selon la revendication 13.
EP14851435.9A 2013-12-17 2014-12-17 Procédé pour produire une couche protectrice sur un composant soumis à des contraintes thermiques, et composant doté d'une couche protectrice de ce type Active EP3084048B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102013021272 2013-12-17
DE102014219819.4A DE102014219819A1 (de) 2014-09-30 2014-09-30 Verfahren zur thermischen Isolierung eines Brennraums und/oder einer Abgasführung einer Brennkraftmaschine
PCT/DE2014/000637 WO2015090267A1 (fr) 2013-12-17 2014-12-17 Procédé pour produire une couche protectrice sur un composant soumis à des contraintes thermiques, et composant doté d'une couche protectrice de ce type

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EP3084048A1 EP3084048A1 (fr) 2016-10-26
EP3084048B1 true EP3084048B1 (fr) 2018-08-01

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DE102015212325A1 (de) * 2015-07-01 2017-01-05 Bosch Mahle Turbo Systems Gmbh & Co. Kg Verfahren zum Herstellen eines Gehäuseteils für eine Turbine eines Abgasturboladers
DE102015120288A1 (de) 2015-11-24 2017-02-16 Meotec GmbH & Co. KG Verfahren zur Erzeugung einer Oberflächenschicht auf einer Oberfläche eines Bauteils mittels plasmaelektrolytischer Oxidation
DE102017206722A1 (de) 2016-04-26 2017-10-26 Ford Global Technologies, Llc Verfahren zur Herstellung einer beschichteten Oberfläche eines tribologischen Systems
CN107541763A (zh) * 2017-10-11 2018-01-05 四川恒诚信电子科技有限公司 一种高导热铝基板的氧化处理方法
DE102017221733A1 (de) 2017-12-01 2019-06-06 Volkswagen Aktiengesellschaft Schichtstapel zur Anordnung in einem Brennraum einer Verbrennungsmaschine, insbesondere eines Kolbens, sowie ein Verfahren zu dessen Herstellung
CN107937965B (zh) * 2017-12-18 2019-07-23 嘉兴学院 一种镁合金阳极氧化电解液及镁合金阳极氧化方法
CN113445100B (zh) * 2021-06-29 2022-07-15 潍柴动力股份有限公司 活塞的制备方法、活塞以及阴极工装
DE102022106581A1 (de) 2022-03-21 2023-09-21 Medical Magnesium GmbH System zur Osteosynthese mit Knochenplatte und Knochenanker aus Magnesiumlegierungen

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CA2479032C (fr) * 2004-09-13 2009-04-21 Jingzeng Zhang Revetement composite a plusieurs fonctions et procede
JP4125765B2 (ja) * 2006-09-28 2008-07-30 日本パーカライジング株式会社 金属のセラミックス皮膜コーティング方法およびそれに用いる電解液ならびにセラミックス皮膜および金属材料
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JP5345155B2 (ja) * 2008-12-26 2013-11-20 日本パーカライジング株式会社 金属の電解セラミックスコーティング方法、金属の電解セラミックスコーティング用電解液および金属材料
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