EP3344801A1 - Improved method for forming a pipe lining of a cylinder head and cylinder head thus obtained - Google Patents

Improved method for forming a pipe lining of a cylinder head and cylinder head thus obtained

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Publication number
EP3344801A1
EP3344801A1 EP16762776.9A EP16762776A EP3344801A1 EP 3344801 A1 EP3344801 A1 EP 3344801A1 EP 16762776 A EP16762776 A EP 16762776A EP 3344801 A1 EP3344801 A1 EP 3344801A1
Authority
EP
European Patent Office
Prior art keywords
cylinder head
cathode
anode
duct
forming
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.)
Withdrawn
Application number
EP16762776.9A
Other languages
German (de)
French (fr)
Inventor
Patrick KÉRAMPRAN
Denis Massinon
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.)
Sifco Applied Surface Concepts
Montupet SA
Original Assignee
Sifco Applied Surface Concepts
Montupet SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sifco Applied Surface Concepts, Montupet SA filed Critical Sifco Applied Surface Concepts
Publication of EP3344801A1 publication Critical patent/EP3344801A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/024Anodisation under pulsed or modulated current or potential
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/005Apparatus specially adapted for electrolytic conversion coating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • C25D11/06Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10Electrodes, e.g. composition, counter electrode
    • C25D17/12Shape or form
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/16Regeneration of process solutions
    • C25D21/18Regeneration of process solutions of electrolytes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F1/00Cylinders; Cylinder heads 
    • F02F1/004Cylinder liners
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F1/00Cylinders; Cylinder heads 
    • F02F1/24Cylinder heads
    • F02F1/42Shape or arrangement of intake or exhaust channels in cylinder heads
    • F02F1/4264Shape or arrangement of intake or exhaust channels in cylinder heads of exhaust channels
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05CINDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2203/00Non-metallic inorganic materials
    • F05C2203/08Ceramics; Oxides
    • F05C2203/0865Oxide ceramics
    • F05C2203/0869Aluminium oxide
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05CINDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00Other material characteristics; Treatment of material
    • F05C2253/12Coating

Definitions

  • the invention relates to a process for forming an aluminum oxide coating on the walls of an aluminum alloy automobile head, and an automobile cylinder head obtained by such a method.
  • the cylinder heads are made of aluminum alloy mainly for reasons of weight gain.
  • the increase in the specific power of recently developed engines imposes on the cylinder head increasingly high thermal loads.
  • the good cooling of the cylinder head is obtained by the integration of cooling circuits inside it, more and more complex, made during the molding of the cylinder head by sand cores.
  • document WO 2013/38249 describes such a process for anodic oxidation of the walls of exhaust ducts of a cylinder head.
  • this method has the disadvantage that the coating thus obtained is porous because of the dissolution of the aluminum during the electrolysis.
  • the presence of these porosities can generate crack primers in particular when the cylinder head is exposed to the usual operating temperatures of the engine, which can reach 250 ° C or more.
  • JP3944788 a process for coating internal conduit cylinder revolution.
  • the treatment disclosed by this document is presented as allowing to confer on the inner surface of the cylinder good abrasion resistance while ensuring good lubrication.
  • the oxide layer thus formed does not limit the heat exchange between the inside of the duct and the walls.
  • teaching of this document is limited to the processing of a cylinder of extremely simple geometry, and the processing of complex geometries is not considered.
  • a unit volume is defined as a volume in which any segment linking in a straight line two points M and N of the volume fully belongs to this volume (in other words: for any pair of points (M, N) of the volume, any point of the segment linking these two points in a straight line also belongs to said volume).
  • a complex volume with ramifications is thus not unitary.
  • the object of the invention is to propose a process for forming an oxide coating in internal cylinder head ducts that do not have the drawbacks of the prior art.
  • an object of the invention is to allow the formation of an oxide coating that does not require post-treatment clogging.
  • Another object of the invention is to provide a method of forming an oxide coating to obtain an improved quality of oxide relative to the prior art.
  • Another object of the invention is to provide a process for forming an oxide coating faster implementation compared to the prior art, compatible with mass production.
  • the subject of the invention is a process for forming an oxide coating on walls of an inner duct of an aluminum alloy casting, comprising the insertion of a cathode into the duct. , circulating an electrolytic solution in said conduit between the cathode and the walls of the anode conduit, and applying a potential difference between the anode and the cathode,
  • the method being characterized in that the application of the potential difference between the anode and the cathode comprises applying a series of DC voltage pulses to the anode.
  • the method according to the invention may further comprise at least one of the following characteristics:
  • each pulse of the series has a duration between 0.01 and 0.02 s and two successive pulses are separated from 0.001 to 0.01 s.
  • the voltage applied to the anode varies during the series of pulses and is between 0 and 150 V to maintain a current density of between 10 and 50 A dm 2 of surface to be treated.
  • the total duration of the series of pulses is between 30 and 300 s depending on the type of alloy to be treated and the desired oxide thickness
  • the electrolyte comprises 10 to 20% of sulfuric acid and 1 to 5% ferrous sulphate.
  • the flow of electrolyte in a conduit is between 0.5 and 2.0 m 3 / h per dm 2 of surface to be treated.
  • the temperature of the electrolyte in a conduit is between -10 ° C and 0 ° C.
  • the cathode is shaped to conform to the shape of the internal duct or ducts of the casting, leaving a mean gap between 3 and 15 mm between the cathode and the duct wall.
  • the subject of the invention is also an aluminum alloy automobile cylinder head, characterized in that it comprises, on the walls of at least one internal duct, an aluminum oxide coating having a thickness of between 50 and 200 ⁇ , adapted to ensure the sealing and thermal insulation of the wall of the internal duct of the cylinder head during the flow, in said duct, exhaust gas at a temperature above 900 ° C.
  • the breech is obtained by implementing the method according to the foregoing description.
  • the internal conduits of the cylinder head provided with an oxide coating are exhaust pipes of combustion products.
  • the pulsed streams also provide a coating of increased quality and non-porous. This coating thus makes it possible to seal the ducts of the cylinder head, which eliminates the need for a post-treatment clogging.
  • composition of the electrolyte contributes to the reduction of the porous character of the coating and thus contributes to its sealing character.
  • the modulation of the electrolyte flow also makes it possible to evacuate at best the calories generated (Joule losses) during the electrolysis in order to limit the phenomenon of dissolution of the oxide layer occurring during the generation of this layer. Maintaining the electrolyte temperature in the desired range improves the quality of the resulting coating layer.
  • Figure 1 schematically a system for implementing a method of forming a coating on a cylinder head according to an embodiment of the invention.
  • Figure 2a shows internal ducts of a cylinder head
  • Figure 2b shows an integrated exhaust manifold cylinder head
  • Figure 3 shows a cathode shaped to correspond to the shape of the internal ducts of a cylinder head.
  • FIG. 4 represents the evolution of the voltage applied to the cylinder head and the current density between the anode and the cathode during the implementation of the insulating coating formation process.
  • FIG. 5 represents an EDS analysis spectrum of the aluminum oxide deposited by the process.
  • FIG. 6 is a sectional illustration of the geometry of an internal automobile cylinder head for which the method of forming a coating according to the invention is suitable.
  • FIG. 7a illustrates a section of thickness observation of the anodizing layer
  • Figure 7b illustrates another thickness observation section of the anodizing layer.
  • FIG. 1 there is shown schematically a casting part 10 of aluminum alloy.
  • This casting piece is of complex geometry and includes internal conduits 1 1 embedded.
  • the constituent alloy of this casting is based on aluminum-silicon hypo-eutectic type, comprising less than 12.5% silicon by mass, and may contain alloying elements such as copper and magnesium .
  • the constituent alloy of this part 10 may be AA319 or an AA356 type alloy.
  • the casting is advantageously a motor yoke 10.
  • the internal ducts 1 1 considered are advantageously exhaust ducts of combustion products.
  • the cylinder head 10 is advantageously a cylinder head comprising an integrated exhaust gas manifold, as is the case, for example, of the cylinder head of FIG. 2b.
  • Figure 2b are also shown the combustion chambers 19 of the cylinder head.
  • FIG. 1 The system 1 used to implement this method is shown in FIG. 1
  • Electrolytic solution circulation system It comprises a cathode 3 disposed inside the cylinder head, a circuit 2 for circulating an electrolytic solution between the cathode and the walls of the ducts of the anode cylinder head, and a control circuit 4 for controlling the potential difference imposed. between the anode and the cathode, said potential difference generating the oxidation reaction at the anode forming the oxide coating.
  • Electrolytic solution circulation system
  • the circulation system 2 of the electrolytic solution in the ducts 1 1 of the cylinder head is shown in FIG. It advantageously comprises an electrolytic solution tank 20, a pump 21, and a closed circuit 22 for circulating the solution between the reservoir and the ducts 1 1 of the cylinder head.
  • the electrolyte solution preferably comprises between 10 and 20% sulfuric acid and 1 to 5% ferrous sulfate.
  • the solution is advantageously maintained at a temperature between -10 ° C and 0 ° C.
  • the circuit 2 advantageously comprises a cooling member 23 of the electrolytic solution.
  • the pump is advantageously variable flow to modulate the flow of electrolyte as a function of temperature.
  • the pump 21 is sized according to the surface to be coated and the thickness of the oxide layer to be grown, and is advantageously adapted to circulate a flow of electrolytic solution in the cylinder head between 0.5 and 2 m 3 per hour and per square decimeter (/ hr dm 2 ) of surface to be treated.
  • a cathode 3 is positioned inside the exhaust ducts 1 1 of the cylinder head.
  • This cathode is made of a material allowing oxidation-reduction reactions to occur in the electrolytic solution.
  • the cathode is advantageously made of stainless steel type 316L for example.
  • the cathode 3 is advantageously shaped so as to match the shape of the ducts 1 1 leaving a gap, preferably constant, between the cathode and the ducts, allowing the circulation of the electrolyte. This makes it possible to establish, when applying a potential difference between the anode and the cathode, current lines homogeneous over an entire surface to be coated, and thus to obtain a growth rate of the identical layer on the surface. This makes it possible to obtain at the end of the process a homogeneous layer thickness on all the treated surfaces.
  • the average gap between the cathode and the wall of a duct is advantageously between 3 and 15 mm. This is a good compromise on the thickness to be maintained between the cathode and the wall of the duct 1 1, firstly to promote the circulation of the electrolyte and the entrainment of the gases generated during the electrolysis, including when the oxide layer has begun to form, and secondly to maintain a current density sufficient to not slow down the growth of the oxide layer.
  • the system for implementing the process for forming a coating layer on the ducts of the cylinder head 10 further comprises a circuit 4 for controlling the potential difference between the anode and the cathode.
  • the circuit 4 comprises a voltage source 40, adapted to deliver a voltage to the anode forming head 10, a control unit 41 of the voltage source, and one or more sensors (not shown) adapted to detect the voltages between the voltage source. anode and the cathode, as well as the current between the anode and the cathode to obtain the defined current.
  • control unit 41 drives the voltage source 40 to deliver a series of DC voltage pulses to the anode.
  • the frequency of the voltage pulses is advantageously greater than 10 Hz, preferably between 10 and 50 Hz.
  • each voltage pulse has a duration of less than 0.1 seconds, and preferably between 0.01 and 0.02 seconds, during which the value of the voltage applied to the anode is constant.
  • Each pulse is further separated from the next pulse by a non-zero time interval of less than 0.1 second, preferably less than 0.01 second, and advantageously between 0.001 and 0.01 second. During this time interval, the voltage applied to the anode is zero.
  • the values of the voltage of each pulse gradually change as the formation of the oxide layer. Indeed, because of its insulating nature, the oxide layer opposes establishing a current between the anode and the cathode.
  • control of the voltage source 40 by the control unit 41 is slaved to the value of the current density between the anode and the cathode.
  • the measurement of the current by the sensors enables the control unit 41 to calculate the current density and, depending on the result, to control the value of the voltage delivered by the voltage source 40.
  • the voltage is generally increasing on the series of pulses.
  • the desired current density is advantageously between 5 and 50 A dm 2 of surface to be treated.
  • the pulses occurring in the first seconds, for example the first 5 or 10 seconds, of the process having a voltage of between 0 and 50 V, and the following pulses advantageously having an increasing voltage up to to reach a voltage sufficient to maintain a current density advantageously greater than 5 A / dm 2 , preferably greater than 10 A / dm 2 .
  • This maximum voltage is advantageously between 70 and 150 V, and preferably between 70 and 120 V.
  • This series of continuous voltage pulses at the anode is implemented for a period of between 30 and 300 s depending on the type of alloy to be treated and the thickness of the oxide layer that is desired get.
  • the formed oxide layer each inner duct advantageously has a thickness advantageously between 50 and 200 ⁇ " ⁇ This thickness varies mainly as a function of the silicon and copper concentration of the treated aluminum alloy, but it remains fine enough not to modify the dimensional characteristics of the product within a tolerance range of ⁇ 0.5 mm.
  • FIGS. 7a and 7b show a sectional view of an oxide coating on a cylinder head obtained as a result of a treatment according to a method according to the invention.
  • the oxide layer is between 34.92 ⁇ and 70.32 ⁇ and has a maximum porosity of 15%. Porosity is understood to mean a global void ratio within the oxide layer.
  • the proposed method thus makes it possible to obtain, in a reduced time, an insulating coating of uniform thickness on internal ducts of aluminum alloy parts such as automobile heads.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Exhaust Silencers (AREA)

Abstract

The invention relates to a method for forming a lining on the walls of an inner pipe of a cast aluminium-alloy part, including inserting a cathode into the pipe, circulating an electrolyte solution in said pipe between the cathode and the walls of the pipe forming an anode, and applying a potential difference between the anode and the cathode, the method being characterised in that applying the potential difference between the anode and the cathode includes applying a series of DC voltage pulses to the anode. The invention also relates to a cylinder head in which the exhaust pipes are lined with a lining obtained by implementing said method.

Description

PROCEDE AMELIORE DE FORMATION D'UN REVETEMENT DE CONDUIT DE IMPROVED METHOD OF FORMING A COIL CONDUIT COATING
CULASSE ET CULASSE AINSI OBTENUE HEAD AND CYLINDER HEAD SO OBTAINED
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
L'invention concerne un procédé de formation d'un revêtement d'oxyde d'aluminium sur des parois d'un conduit interne de culasse automobile en alliage d'aluminium, et une culasse automobile obtenue par un tel procédé. ETAT DE LA TECHNIQUE  The invention relates to a process for forming an aluminum oxide coating on the walls of an aluminum alloy automobile head, and an automobile cylinder head obtained by such a method. STATE OF THE ART
Les culasses automobiles sont réalisées en alliage d'aluminium essentiellement pour des raisons de gain de masse. L'augmentation de la puissance spécifique des moteurs développés récemment impose sur la culasse des sollicitations thermiques de plus en plus élevées.  The cylinder heads are made of aluminum alloy mainly for reasons of weight gain. The increase in the specific power of recently developed engines imposes on the cylinder head increasingly high thermal loads.
Le bon refroidissement de la culasse est obtenu par l'intégration de circuits de refroidissement à l'intérieur de celle-ci, de plus en plus complexes, réalisés au cours du moulage de la culasse par des noyaux en sable.  The good cooling of the cylinder head is obtained by the integration of cooling circuits inside it, more and more complex, made during the molding of the cylinder head by sand cores.
Ceci permet dans une certaine mesure de compenser l'élévation de température générée par l'augmentation de puissance spécifique du moteur, mais s'avère de plus en plus souvent insuffisant, et de plus impose de modifier la géométrie des conduits intérieurs des culasses.  This makes it possible, to a certain extent, to compensate for the rise in temperature generated by the increase in specific power of the engine, but proves to be more and more often insufficient, and moreover it is necessary to modify the geometry of the interior ducts of the cylinder heads.
Pour limiter encore l'élévation de température de la culasse, il a été proposé des procédés électrochimiques permettant de former, sur les parois de conduits intérieurs des culasses, par exemple des conduits d'échappement, un revêtement d'oxyde, afin de limiter les échanges thermiques entre la culasse et le conduit (par exemple les gaz d'échappement présents dans le conduit).  To further limit the temperature rise of the cylinder head, it has been proposed electrochemical processes for forming, on the interior duct walls of the cylinder heads, for example exhaust ducts, an oxide coating, in order to limit the heat exchanges between the cylinder head and the duct (for example the exhaust gases present in the duct).
Ceci permet d'une part de réduire la température de la culasse, et d'autre part d'augmenter la température des gaz à la sortie de la culasse, ce qui améliore le rendement du moteur, sans impacter la géométrie des conduits.  This makes it possible on the one hand to reduce the temperature of the cylinder head and, on the other hand, to increase the temperature of the gases at the outlet of the cylinder head, which improves the efficiency of the engine, without impacting the geometry of the pipes.
Par exemple le document WO 2013/38249 décrit un tel procédé d'oxydation anodique des parois de conduits d'échappement d'une culasse.  For example, document WO 2013/38249 describes such a process for anodic oxidation of the walls of exhaust ducts of a cylinder head.
Cependant, ce procédé présente l'inconvénient que le revêtement ainsi obtenu est poreux du fait de la dissolution de l'aluminium lors de l'électrolyse. La présence de ces porosités peut générer des amorces de fissures en particulier lorsque la culasse est exposée aux températures usuelles de fonctionnement du moteur, qui peuvent atteindre 250°C ou plus. However, this method has the disadvantage that the coating thus obtained is porous because of the dissolution of the aluminum during the electrolysis. The presence of these porosities can generate crack primers in particular when the cylinder head is exposed to the usual operating temperatures of the engine, which can reach 250 ° C or more.
Il peut en résulter des fuites entre les circuits d'eau ou de liquide de refroidissement se trouvant dans le voisinage immédiat des conduits d'échappement vers ces conduits, ce qui peut entraîner la ruine du moteur.  This can result in leaks between the water or coolant circuits in the immediate vicinity of the exhaust ducts to these ducts, which can lead to engine failure.
Il est donc nécessaire d'effectuer un post-traitement de colmatage du revêtement d'oxyde, ce qui rend le procédé plus long et plus coûteux.  It is therefore necessary to carry out a post-treatment clogging of the oxide coating, which makes the process longer and more expensive.
Par ailleurs, on connaît du document JP3944788 un processus de revêtement de conduit interne de cylindre de révolution. Le traitement divulgué par ce document est présenté comme permettant de conférer à la surface interne du cylindre une bonne résistance à l'abrasion tout en assurant une bonne lubrification. La couche d'oxyde ainsi formée ne permet pas de limiter les échanges thermiques entre l'intérieur du conduit et les parois. Par ailleurs, l'enseignement de ce document est limité au traitement d'un cylindre de géométrie extrêmement simple, et le traitement de géométries complexes n'est aucunement envisagé.  Furthermore, it is known from JP3944788 a process for coating internal conduit cylinder revolution. The treatment disclosed by this document is presented as allowing to confer on the inner surface of the cylinder good abrasion resistance while ensuring good lubrication. The oxide layer thus formed does not limit the heat exchange between the inside of the duct and the walls. Moreover, the teaching of this document is limited to the processing of a cylinder of extremely simple geometry, and the processing of complex geometries is not considered.
Le document US 2013/0146041 décrit un autre procédé, qui ne mentionne pas l'application d'impulsions de tension continue.  Document US 2013/0146041 describes another method, which does not mention the application of DC voltage pulses.
Le procédé divulgué par ce document est également limité à une géométrie simple de cylindre. Dans le document JP3944788 comme dans le document US 2013/0146041 , la surface à revêtir s'étend ainsi autour d'un volume unitaire.  The method disclosed by this document is also limited to a simple cylinder geometry. In document JP3944788 as in document US 2013/0146041, the surface to be coated thus extends around a unit volume.
Dans le présent texte, et comme illustré sur la figure A, un volume unitaire est défini comme un volume dans lequel tout segment liant en ligne droite deux points M et N du volume appartient intégralement à ce volume (en d'autres termes : pour toute paire de points (M,N) du volume, tout point du segment liant ces deux points en ligne droite appartient également audit volume). Un volume complexe présentant des ramifications n'est ainsi pas unitaire.  In the present text, and as illustrated in FIG. A, a unit volume is defined as a volume in which any segment linking in a straight line two points M and N of the volume fully belongs to this volume (in other words: for any pair of points (M, N) of the volume, any point of the segment linking these two points in a straight line also belongs to said volume). A complex volume with ramifications is thus not unitary.
Les procédés décrits dans JP3944788 et US 2013/0146041 ne seraient donc pas applicables aux géométries complexes, notamment de culasse.  The methods described in JP3944788 and US 2013/0146041 would therefore not be applicable to complex geometries, including cylinder head.
Ces procédés ne sont par ailleurs pas susceptibles de donner accès à des couches d'oxyde d'aluminium de faible porosité, et de faible épaisseur.  These processes are also not likely to give access to aluminum oxide layers of low porosity, and thin.
Il existe donc un besoin pour une solution permettant de limiter les échanges thermiques entre les gaz d'échappement et la culasse ne présentant pas ces inconvénients. PRESENTATION DE L'INVENTION There is therefore a need for a solution to limit the heat exchange between the exhaust and the cylinder head does not have these disadvantages. PRESENTATION OF THE INVENTION
L'invention a pour but de proposer un procédé de formation d'un revêtement d'oxyde dans des conduits intérieurs de culasse ne présentant pas les inconvénients de l'art antérieur.  The object of the invention is to propose a process for forming an oxide coating in internal cylinder head ducts that do not have the drawbacks of the prior art.
En particulier, un but de l'invention est de permettre la formation d'un revêtement d'oxyde ne nécessitant pas de post-traitement de colmatage.  In particular, an object of the invention is to allow the formation of an oxide coating that does not require post-treatment clogging.
Un autre but de l'invention est de proposer un procédé de formation d'un revêtement d'oxyde permettant d'obtenir une qualité améliorée d'oxyde par rapport à l'art antérieur.  Another object of the invention is to provide a method of forming an oxide coating to obtain an improved quality of oxide relative to the prior art.
Un autre but de l'invention est de proposer un procédé de formation d'un revêtement d'oxyde de mise en œuvre plus rapide par rapport à l'art antérieur, compatible avec une production en grande série.  Another object of the invention is to provide a process for forming an oxide coating faster implementation compared to the prior art, compatible with mass production.
A cet égard, l'invention a pour objet un procédé de formation d'un revêtement d'oxyde sur des parois d'un conduit interne de pièce de fonderie en alliage d'aluminium, comprenant l'insertion d'une cathode dans le conduit, la mise en circulation d'une solution électrolytique dans ledit conduit entre la cathode et les parois du conduit formant anode, et l'application d'une différence de potentiel entre l'anode et la cathode, In this regard, the subject of the invention is a process for forming an oxide coating on walls of an inner duct of an aluminum alloy casting, comprising the insertion of a cathode into the duct. , circulating an electrolytic solution in said conduit between the cathode and the walls of the anode conduit, and applying a potential difference between the anode and the cathode,
le procédé étant caractérisé en ce que l'application de la différence de potentiel entre l'anode et la cathode comprend l'application d'une série d'impulsions de tension continue à l'anode. the method being characterized in that the application of the potential difference between the anode and the cathode comprises applying a series of DC voltage pulses to the anode.
Avantageusement, mais facultativement, le procédé selon l'invention peut en outre comprendre au moins l'une des caractéristiques suivantes : Advantageously, but optionally, the method according to the invention may further comprise at least one of the following characteristics:
chaque impulsion de la série présente une durée comprise entre 0.01 et 0.02 s et deux impulsions successives sont séparées de 0.001 à 0.01 s.  each pulse of the series has a duration between 0.01 and 0.02 s and two successive pulses are separated from 0.001 to 0.01 s.
la tension appliquée à l'anode varie lors de la série d'impulsions et est comprise entre 0 et 150 V pour maintenir une densité de courant comprise entre 10 et 50 A dm2 de surface à traiter. the voltage applied to the anode varies during the series of pulses and is between 0 and 150 V to maintain a current density of between 10 and 50 A dm 2 of surface to be treated.
la durée totale de la série d'impulsions est comprise entre 30 et 300 s en fonction du type d'alliage à traiter et de l'épaisseur d'oxyde souhaitée, l'électrolyte comprend 10 à 20% d'acide sulfurique et 1 à 5% de sulfate ferreux. le débit d'électrolyte dans un conduit est compris entre 0.5 et 2,0 m3/h par dm2 de surface à traiter. the total duration of the series of pulses is between 30 and 300 s depending on the type of alloy to be treated and the desired oxide thickness, the electrolyte comprises 10 to 20% of sulfuric acid and 1 to 5% ferrous sulphate. the flow of electrolyte in a conduit is between 0.5 and 2.0 m 3 / h per dm 2 of surface to be treated.
la température de l'électrolyte dans un conduit est comprise entre -10°C et 0 °C.  the temperature of the electrolyte in a conduit is between -10 ° C and 0 ° C.
- la cathode est conformée pour épouser la forme du ou des conduits internes de la pièce de fonderie, en laissant un interstice moyen compris entre 3 et 15 mm entre la cathode et la paroi du conduit.  - The cathode is shaped to conform to the shape of the internal duct or ducts of the casting, leaving a mean gap between 3 and 15 mm between the cathode and the duct wall.
L'invention a également pour objet une culasse automobile en alliage d'aluminium caractérisée en ce qu'elle comprend, sur les parois d'au moins un conduit interne, un revêtement d'oxyde d'aluminium d'une épaisseur comprise entre 50 et 200 μηι, adapté pour assurer l'étanchéité et l'isolation thermique de la paroi du conduit interne de la culasse lors de l'écoulement, dans ledit conduit, gaz d'échappement à une température supérieure à 900 °C. The subject of the invention is also an aluminum alloy automobile cylinder head, characterized in that it comprises, on the walls of at least one internal duct, an aluminum oxide coating having a thickness of between 50 and 200 μηι, adapted to ensure the sealing and thermal insulation of the wall of the internal duct of the cylinder head during the flow, in said duct, exhaust gas at a temperature above 900 ° C.
Avantageusement, la culasse automobile est obtenue par la mise en œuvre du procédé selon la description qui précède. Advantageously, the breech is obtained by implementing the method according to the foregoing description.
Dans un mode de réalisation, les conduits internes de la culasse pourvus d'un revêtement d'oxyde sont des conduits d'échappement de produits de combustion.  In one embodiment, the internal conduits of the cylinder head provided with an oxide coating are exhaust pipes of combustion products.
L'utilisation de courants puisés lors du traitement d'anodisation de la culasse permet d'obtenir plus rapidement un revêtement d'épaisseur déterminé. The use of pulsed currents during the anodizing treatment of the cylinder head makes it possible to obtain a coating of a predetermined thickness more rapidly.
En outre, les courants puisés permettent également d'obtenir un revêtement de qualité accrue et non poreux. Ce revêtement permet donc d'assurer l'étanchéité des conduits de la culasse, ce qui supprime la nécessité d'un post-traitement de colmatage.  In addition, the pulsed streams also provide a coating of increased quality and non-porous. This coating thus makes it possible to seal the ducts of the cylinder head, which eliminates the need for a post-treatment clogging.
L'utilisation d'une cathode dont la géométrie est conforme à celle du conduit interne de la culasse à revêtir permet de générer des lignes de courant homogènes sur l'ensemble du conduit et ainsi un revêtement d'épaisseur homogène au terme du traitement. Il est à noter que la géométrie des conduits internes de culasse est complexe, comme illustrée sur la figure 6. Sur cette figure en coupe on remarque la présence de ramifications multiples à partir d'une ouverture de base débouchant dans la chambre de combustion (non illustrée). Chaque branche s'étend à partir de cette base avec des courbures différentes selon leur éloignement à l'axe de symétrie X-X de la structure, passant par l'ouverture de base. On comprend donc de cette illustration que l'obtention d'un revêtement d'épaisseur homogène dans tout le conduit nécessite un processus de traitement qui ménage des lignes de courant homogènes à tout instant. Le procédé selon l'invention répond à ces nécessités. The use of a cathode whose geometry is consistent with that of the internal duct of the cylinder head to be coated allows to generate homogeneous streamlines on the entire duct and thus a coating of uniform thickness at the end of the treatment. It should be noted that the geometry of the internal cylinder head ducts is complex, as shown in FIG. 6. In this sectional figure, the presence of multiple branches from a base opening opening into the combustion chamber (no shown). Each branch extends from this base with different curvatures according to their distance to the axis of symmetry XX of the structure, passing through the base opening. It is therefore clear from this illustration that obtaining a coating of uniform thickness throughout the duct requires a treatment process that ensures homogeneous current lines at all times. The method according to the invention meets these needs.
Le choix de la composition de l'électrolyte contribue à la réduction du caractère poreux du revêtement et contribue donc à son caractère étanche.  The choice of the composition of the electrolyte contributes to the reduction of the porous character of the coating and thus contributes to its sealing character.
La modulation du débit d'électrolyte permet également d'évacuer au mieux les calories générées (pertes Joules) lors de l'électrolyse pour limiter le phénomène de dissolution de couche d'oxyde survenant lors de la génération de cette couche. Le maintien de la température d'électrolyte dans la plage voulue permet d'améliorer la qualité de la couche de revêtement obtenue.  The modulation of the electrolyte flow also makes it possible to evacuate at best the calories generated (Joule losses) during the electrolysis in order to limit the phenomenon of dissolution of the oxide layer occurring during the generation of this layer. Maintaining the electrolyte temperature in the desired range improves the quality of the resulting coating layer.
DESCRIPTION DES FIGURES DESCRIPTION OF THE FIGURES
D'autres caractéristiques, buts et avantages de l'invention ressortiront de la description qui suit, qui est purement illustrative et non limitative, et qui doit être lue en regard des dessins annexés sur lesquels, outre la figure A qui illustre la notion de volume unitaire :  Other characteristics, objects and advantages of the invention will emerge from the description which follows, which is purely illustrative and nonlimiting, and which should be read with reference to the appended drawings in which, in addition to FIG. unitary:
La figure 1 schématiquement un système pour la mise en œuvre d'un procédé de formation de revêtement sur une culasse conformément à un mode de réalisation de l'invention.  Figure 1 schematically a system for implementing a method of forming a coating on a cylinder head according to an embodiment of the invention.
La figure 2a représente des conduits internes d'une culasse, et la figure 2b représente une culasse à collecteur de gaz d'échappement intégré. La figure 3 représente une cathode conformée pour correspondre à la forme des conduits internes d'une culasse.  Figure 2a shows internal ducts of a cylinder head, and Figure 2b shows an integrated exhaust manifold cylinder head. Figure 3 shows a cathode shaped to correspond to the shape of the internal ducts of a cylinder head.
La figure 4 représente l'évolution de la tension appliquée à la culasse et la densité de courant entre l'anode et la cathode lors de la mise en œuvre du procédé de formation du revêtement isolant.  FIG. 4 represents the evolution of the voltage applied to the cylinder head and the current density between the anode and the cathode during the implementation of the insulating coating formation process.
La figure 5 représente un spectre d'analyse EDS de l'oxyde d'aluminium déposé par le procédé.  FIG. 5 represents an EDS analysis spectrum of the aluminum oxide deposited by the process.
La figure 6 est une illustration en coupe de la géométrie d'un conduit interne de culasse automobile pour laquelle le procédé de formation d'un revêtement selon l'invention est adapté. La figure 7a illustre une coupe d'observation d'épaisseur de la couche d'anodisation Figure 6 is a sectional illustration of the geometry of an internal automobile cylinder head for which the method of forming a coating according to the invention is suitable. FIG. 7a illustrates a section of thickness observation of the anodizing layer
La figure 7b illustre une autre coupe d'observation d'épaisseur de la couche d'anodisation.  Figure 7b illustrates another thickness observation section of the anodizing layer.
DESCRIPTION DETAILLEE D'AU MOINS UN MODE DE MISE EN ŒUVRE DE L'INVENTION DETAILED DESCRIPTION OF AT LEAST ONE MODE OF IMPLEMENTING THE INVENTION
En référence à la figure 1 , on a représenté schématiquement une pièce de fonderie 10 en alliage d'aluminium. Cette pièce de fonderie est de géométrie complexe et comprend notamment des conduits internes 1 1 noyautés.  Referring to Figure 1, there is shown schematically a casting part 10 of aluminum alloy. This casting piece is of complex geometry and includes internal conduits 1 1 embedded.
L'alliage constitutif de cette pièce de fonderie est à base d'aluminium-silicium de type hypo-eutectique, comprenant moins de 12,5% de silicium en masse, et pouvant contenir des éléments d'alliage tels que du cuivre et du magnésium.  The constituent alloy of this casting is based on aluminum-silicon hypo-eutectic type, comprising less than 12.5% silicon by mass, and may contain alloying elements such as copper and magnesium .
A titre d'exemple non limitatif, l'alliage constitutif de cette pièce 10 peut être de type AA319 ou un alliage de type AA356.  By way of non-limiting example, the constituent alloy of this part 10 may be AA319 or an AA356 type alloy.
Comme représenté sur la figure 2, la pièce de fonderie est avantageusement une culasse de moteur 10. Dans ce cas, les conduits internes 1 1 considérés sont avantageusement des conduits d'échappement de produits de combustion. A cet égard, la culasse 10 est avantageusement une culasse comprenant un collecteur de gaz d'échappement intégré, comme c'est le cas par exemple de la culasse de la figure 2b. Sur la figure 2b sont également représentées les chambres de combustion 19 de la culasse.  As shown in FIG. 2, the casting is advantageously a motor yoke 10. In this case, the internal ducts 1 1 considered are advantageously exhaust ducts of combustion products. In this respect, the cylinder head 10 is advantageously a cylinder head comprising an integrated exhaust gas manifold, as is the case, for example, of the cylinder head of FIG. 2b. In Figure 2b are also shown the combustion chambers 19 of the cylinder head.
Afin de limiter les échanges thermiques entre les gaz d'échappement qui circulent dans le conduit 1 1 , dont la température peut dépasser les 900°C, et la pièce 10, on met en œuvre un procédé de formation d'un revêtement isolant 13 en oxyde d'aluminium sur les parois internes de chaque conduit 1 1 par oxydation anodique.  In order to limit the heat exchange between the exhaust gases flowing in the duct 11, whose temperature may exceed 900 ° C., and the piece 10, a method of forming an insulating coating 13 is implemented. aluminum oxide on the inner walls of each pipe 1 1 by anodic oxidation.
Le système 1 utilisé pour mettre en œuvre ce procédé est représenté sur la figure 1.  The system 1 used to implement this method is shown in FIG.
II comprend une cathode 3 disposée à l'intérieur de la culasse, un circuit 2 de circulation d'une solution électrolytique entre la cathode et les parois des conduits de la culasse formant anode, et un circuit 4 de commande de la différence de potentiel imposée entre l'anode et la cathode, ladite différence de potentiel engendrant la réaction d'oxydation à l'anode formant le revêtement d'oxyde. Système de circulation de solution électrolytigue It comprises a cathode 3 disposed inside the cylinder head, a circuit 2 for circulating an electrolytic solution between the cathode and the walls of the ducts of the anode cylinder head, and a control circuit 4 for controlling the potential difference imposed. between the anode and the cathode, said potential difference generating the oxidation reaction at the anode forming the oxide coating. Electrolytic solution circulation system
Le système 2 de circulation de la solution électrolytique dans les conduits 1 1 de la culasse est représenté sur la figure 1 . Il comprend avantageusement un réservoir de solution électrolytique 20, une pompe 21 , et un circuit fermé 22 de circulation de solution entre le réservoir et les conduits 1 1 de la culasse. La solution électrolytique comprend de préférence entre 10 et 20% d'acide sulfurique et de 1 à 5% de sulfate ferreux.  The circulation system 2 of the electrolytic solution in the ducts 1 1 of the cylinder head is shown in FIG. It advantageously comprises an electrolytic solution tank 20, a pump 21, and a closed circuit 22 for circulating the solution between the reservoir and the ducts 1 1 of the cylinder head. The electrolyte solution preferably comprises between 10 and 20% sulfuric acid and 1 to 5% ferrous sulfate.
Pour éviter une dissolution de l'oxyde créé lors du procédé de formation du revêtement, cette dissolution étant catalysée par la chaleur occasionnée par l'électrolyse, la solution est avantageusement maintenue à une température comprise entre -10°C et 0°C.  To avoid dissolution of the oxide created during the coating forming process, this dissolution being catalysed by the heat caused by the electrolysis, the solution is advantageously maintained at a temperature between -10 ° C and 0 ° C.
A cet égard, le circuit 2 comprend avantageusement un organe de refroidissement 23 de la solution électrolytique. De plus, la pompe est avantageusement à débit variable pour moduler le débit d'électrolyte en fonction de la température.  In this respect, the circuit 2 advantageously comprises a cooling member 23 of the electrolytic solution. In addition, the pump is advantageously variable flow to modulate the flow of electrolyte as a function of temperature.
Avantageusement, la pompe 21 est dimensionnée en fonction de la surface à revêtir et de l'épaisseur de la couche d'oxyde à faire croître, et est avantageusement adaptée pour faire circuler un débit de solution électrolytique dans la culasse compris entre 0,5 et 2 m3 par heure et par décimètre carré (/h. dm2) de surface à traiter. Advantageously, the pump 21 is sized according to the surface to be coated and the thickness of the oxide layer to be grown, and is advantageously adapted to circulate a flow of electrolytic solution in the cylinder head between 0.5 and 2 m 3 per hour and per square decimeter (/ hr dm 2 ) of surface to be treated.
La circulation d'électrolyte dans les conduits à température comprise entre - 10 et 0 °C permet d'obtenir un revêtement homogène. Disposition de la cathode  The circulation of electrolyte in the ducts at a temperature between -10 and 0 ° C makes it possible to obtain a homogeneous coating. Cathode layout
Une cathode 3 est positionnée à l'intérieur des conduits d'échappement 1 1 de la culasse. Cette cathode est réalisée en un matériau permettant à des réactions d'oxydo-réduction de se produire dans la solution électrolytique. En particulier, la cathode est avantageusement réalisée en acier inoxydable de type 316L par exemple.  A cathode 3 is positioned inside the exhaust ducts 1 1 of the cylinder head. This cathode is made of a material allowing oxidation-reduction reactions to occur in the electrolytic solution. In particular, the cathode is advantageously made of stainless steel type 316L for example.
En référence à la figure 3, la cathode 3 est avantageusement conformée de manière à épouser la forme des conduits 1 1 en laissant un interstice, de préférence constant, entre la cathode et les conduits, permettant la circulation de l'électrolyte. Ceci permet d'établir, lors de l'application d'une différence de potentiel entre l'anode et la cathode, des lignes de courant homogènes sur l'ensemble d'une surface à revêtir, et ainsi d'obtenir une vitesse de croissance de la couche identique sur la surface. Ceci permet d'obtenir à l'issue du procédé une épaisseur de couche homogène sur toutes les surfaces traitées. Referring to Figure 3, the cathode 3 is advantageously shaped so as to match the shape of the ducts 1 1 leaving a gap, preferably constant, between the cathode and the ducts, allowing the circulation of the electrolyte. This makes it possible to establish, when applying a potential difference between the anode and the cathode, current lines homogeneous over an entire surface to be coated, and thus to obtain a growth rate of the identical layer on the surface. This makes it possible to obtain at the end of the process a homogeneous layer thickness on all the treated surfaces.
L'interstice moyen entre la cathode et la paroi d'un conduit est avantageusement compris entre 3 et 15 mm. Ceci constitue un bon compromis sur l'épaisseur à maintenir entre la cathode et la paroi du conduit 1 1 , d'une part pour favoriser la circulation de l'électrolyte et l'entraînement des gaz générés lors de l'électrolyse, y compris lorsque la couche d'oxyde a commencé à se former, et d'autre part pour maintenir une densité de courant suffisante pour ne pas ralentir la croissance de la couche d'oxyde.  The average gap between the cathode and the wall of a duct is advantageously between 3 and 15 mm. This is a good compromise on the thickness to be maintained between the cathode and the wall of the duct 1 1, firstly to promote the circulation of the electrolyte and the entrainment of the gases generated during the electrolysis, including when the oxide layer has begun to form, and secondly to maintain a current density sufficient to not slow down the growth of the oxide layer.
Oxydation anodigue Anodal oxidation
De retour à la figure 1 , le système pour la mise en œuvre du procédé de formation d'une couche de revêtement sur les conduits de la culasse 10 comprend en outre un circuit 4 de commande de la différence de potentiel entre l'anode et la cathode.  Returning to FIG. 1, the system for implementing the process for forming a coating layer on the ducts of the cylinder head 10 further comprises a circuit 4 for controlling the potential difference between the anode and the cathode.
Le circuit 4 comprend une source de tension 40, adaptée pour délivrer une tension à la culasse 10 formant anode, une unité de commande 41 de la source de tension, et un ou plusieurs capteurs (non représentés) adaptés pour relever les tensions entre l'anode et la cathode, ainsi que le courant entre l'anode et la cathode pour permettre l'obtention du courant défini.  The circuit 4 comprises a voltage source 40, adapted to deliver a voltage to the anode forming head 10, a control unit 41 of the voltage source, and one or more sensors (not shown) adapted to detect the voltages between the voltage source. anode and the cathode, as well as the current between the anode and the cathode to obtain the defined current.
En référence à la figure 4, pour former la couche 13 d'oxyde sur les parois des conduits 1 1 , l'unité de commande 41 pilote la source de tension 40 pour délivrer à l'anode une série d'impulsions de tension continue.  With reference to FIG. 4, to form the oxide layer 13 on the walls of the conduits 1 1, the control unit 41 drives the voltage source 40 to deliver a series of DC voltage pulses to the anode.
La fréquence des impulsions de tensions est avantageusement supérieure à 10 Hz, de préférence comprise entre 10 et 50 Hz.  The frequency of the voltage pulses is advantageously greater than 10 Hz, preferably between 10 and 50 Hz.
Plus précisément, chaque impulsion de tension présente une durée inférieure à 0,1 seconde, et de préférence comprise entre 0,01 et 0,02 seconde, pendant laquelle la valeur de la tension appliquée à l'anode est constante. Chaque impulsion est de plus séparée de l'impulsion suivante par un intervalle de temps non nul inférieur à 0,1 seconde, de préférence inférieur à 0,01 seconde, et avantageusement compris entre 0,001 et 0,01 seconde. Au cours de cet intervalle de temps, la tension appliquée à l'anode est donc nulle. L'application d'une telle série d'impulsions de tension permet de diminuer le temps nécessaire à la mise en œuvre du procédé en favorisant l'évacuation des pertes Joules et des gaz. More specifically, each voltage pulse has a duration of less than 0.1 seconds, and preferably between 0.01 and 0.02 seconds, during which the value of the voltage applied to the anode is constant. Each pulse is further separated from the next pulse by a non-zero time interval of less than 0.1 second, preferably less than 0.01 second, and advantageously between 0.001 and 0.01 second. During this time interval, the voltage applied to the anode is zero. The application of such a series of voltage pulses makes it possible to reduce the time required to implement the process by promoting the evacuation of Joule losses and gases.
A titre comparatif, l'obtention d'une couche d'oxyde d'une épaisseur comprise entre 50 et 200 μηη nécessite une durée de traitement de l'ordre de 70 secondes, tandis que la durée requise dans l'art antérieur était de l'ordre de plusieurs minutes.  By way of comparison, obtaining an oxide layer with a thickness of between 50 and 200 μηη requires a processing time of the order of 70 seconds, whereas the time required in the prior art was order of several minutes.
De plus, les valeurs de la tension de chaque impulsion évoluent progressivement au fur et à mesure de la formation de la couche d'oxyde. En effet, du fait de son caractère isolant, la couche d'oxyde s'oppose à l'établissant d'un courant entre l'anode et la cathode.  In addition, the values of the voltage of each pulse gradually change as the formation of the oxide layer. Indeed, because of its insulating nature, the oxide layer opposes establishing a current between the anode and the cathode.
En particulier, le pilotage de la source de tension 40 par l'unité de commande 41 est asservi à la valeur de la densité de courant entre l'anode et la cathode. La mesure du courant par les capteurs permet à l'unité de commande 41 de calculer la densité de courant et, en fonction du résultat, de piloter la valeur de la tension délivrée par la source de tension 40.  In particular, the control of the voltage source 40 by the control unit 41 is slaved to the value of the current density between the anode and the cathode. The measurement of the current by the sensors enables the control unit 41 to calculate the current density and, depending on the result, to control the value of the voltage delivered by the voltage source 40.
Pour maintenir une densité de courant suffisante pour poursuivre la croissance de la couche, la tension est globalement croissante sur la série d'impulsions. La densité de courant recherchée est avantageusement comprise entre 5 et 50 A dm2 de surface à traiter. To maintain a current density sufficient to continue the growth of the layer, the voltage is generally increasing on the series of pulses. The desired current density is advantageously between 5 and 50 A dm 2 of surface to be treated.
Ainsi la valeur de la tension de chaque impulsion est comprise entre 0 et Thus the value of the voltage of each pulse is between 0 and
150V, avantageusement entre 0 et 120 V, les impulsions survenant dans les premières secondes, par exemple les 5 ou 10 premières secondes, du procédé présentant une tension comprise entre 0 et 50 V, et les impulsions suivantes présentant avantageusement une tension croissante jusqu'à atteindre une tension suffisante pour maintenir une densité de courant avantageusement supérieure à 5 A/dm2, de préférence supérieure à 10 A/dm2. Cette tension maximale est avantageusement comprise entre 70 et 150 V, et de préférence entre 70 et 120 V. 150 V, advantageously between 0 and 120 V, the pulses occurring in the first seconds, for example the first 5 or 10 seconds, of the process having a voltage of between 0 and 50 V, and the following pulses advantageously having an increasing voltage up to to reach a voltage sufficient to maintain a current density advantageously greater than 5 A / dm 2 , preferably greater than 10 A / dm 2 . This maximum voltage is advantageously between 70 and 150 V, and preferably between 70 and 120 V.
Cette série d'impulsions de tension continue à l'anode est mise en œuvre pendant une durée comprise entre 30 et 300 s en fonction du type d'alliage à traiter et de l'épaisseur de la couche d'oxyde que l'on souhaite obtenir.  This series of continuous voltage pulses at the anode is implemented for a period of between 30 and 300 s depending on the type of alloy to be treated and the thickness of the oxide layer that is desired get.
Ainsi l'application d'un potentiel à l'anode génère une différence de potentiel entre la culasse et la cathode, à l'origine de réactions chimiques produisant, à partir de l'aluminium de la culasse, un oxyde d'aluminium sur les parois des conduits d'échappement 1 1 . On a représenté à la figure 5 un spectre d'analyse EDS (Energy Dispersive Spectroscopy) réalisé sur l'oxyde d'aluminium ainsi réalisé. Les hauteurs relatives des pics de ce spectre indiquent une composition de l'oxyde proche en stoechiométrie de celle de l'alumine Al203, les autres composants étant des polluants provenant de la composition électrolytique. Thus the application of a potential at the anode generates a potential difference between the cylinder head and the cathode, at the origin of chemical reactions producing, from the aluminum of the cylinder head, an aluminum oxide on the Exhaust duct walls 1 1. There is shown in Figure 5 an EDS (Energy Dispersive Spectroscopy) analysis spectrum produced on the aluminum oxide thus produced. The relative heights of the peaks of this spectrum indicate a composition of the oxide near stoichiometric that of Al 2 O 3 alumina, the other components being pollutants from the electrolytic composition.
Pour que la couche d'oxyde 13 assure l'isolation de la culasse en fonctionnement, c'est-à-dire lorsque des gaz d'une température de 950°C s'écoulent dans les conduits internes, la couche d'oxyde formée sur chaque conduit interne présente avantageusement une épaisseur comprise avantageusement entre 50 et 200μη"ΐ. Cette épaisseur varie principalement en fonction de la concentration en silicium et en cuivre de l'alliage d'aluminium traité. Elle reste toutefois suffisamment fine pour ne pas modifier les caractéristiques dimensionnelles du produit, dans un intervalle de tolérance de ± 0.5 mm.  So that the oxide layer 13 ensures the insulation of the cylinder head in operation, that is to say when gases with a temperature of 950 ° C flow in the internal conduits, the formed oxide layer each inner duct advantageously has a thickness advantageously between 50 and 200μη "ΐ This thickness varies mainly as a function of the silicon and copper concentration of the treated aluminum alloy, but it remains fine enough not to modify the dimensional characteristics of the product within a tolerance range of ± 0.5 mm.
Il a été mis en évidence que l'application d'un traitement thermique de type T7, c'est-à-dire comportant une mise en solution à une température comprise entre 490 et 540°C (en fonction de l'alliage d'aluminium utilisé), une trempe à l'eau ou à l'air, et un revenu à une température égale ou supérieure à 200°C, permettait d'obtenir des couches de revêtement plus homogènes en épaisseur et densité.  It has been demonstrated that the application of a heat treatment of the T7 type, that is to say comprising a dissolution at a temperature of between 490 and 540 ° C. (depending on the alloy of aluminum used), quenching with water or air, and tempering at a temperature equal to or greater than 200 ° C, made it possible to obtain more homogeneous coating layers in thickness and density.
A titre illustratif et de manière non limitative, les figures 7a et 7b montrent une vue en coupe d'un revêtement d'oxyde sur une culasse obtenu à la suite d'un traitement selon un procédé conforme à l'invention. Sur ces illustrations, la couche d'oxyde est comprise entre 34,92 μηη et 70,32 μηη et présente une porosité maximale de 15%. On comprend par porosité un taux de vide global au sein de la couche d'oxyde.  By way of illustration and in a nonlimiting manner, FIGS. 7a and 7b show a sectional view of an oxide coating on a cylinder head obtained as a result of a treatment according to a method according to the invention. In these illustrations, the oxide layer is between 34.92 μηη and 70.32 μηη and has a maximum porosity of 15%. Porosity is understood to mean a global void ratio within the oxide layer.
On obtient ainsi une bonne densité de couche d'une part et une faible épaisseur d'autre part. Ainsi, il n'est plus nécessaire d'effectuer de traitement postérieur de colmatage, ni d'usinage de reprise ou de finition. Par ailleurs, le procédé ainsi décrit conduit à des temps de cycle compatibles avec la production industrielle en grande série du secteur automobile (soit 5 à 6 min).  This gives a good layer density on the one hand and a small thickness on the other hand. Thus, it is no longer necessary to perform subsequent sealing treatment, or recovery or finishing machining. Moreover, the process thus described leads to cycle times compatible with industrial mass production in the automotive sector (ie 5 to 6 minutes).
Le procédé proposé permet ainsi d'obtenir en un temps réduit un revêtement isolant et d'épaisseur homogène sur des conduits internes de pièces en alliage d'aluminium telles que des culasses automobiles.  The proposed method thus makes it possible to obtain, in a reduced time, an insulating coating of uniform thickness on internal ducts of aluminum alloy parts such as automobile heads.

Claims

REVENDICATIONS
1 . Procédé de formation d'un revêtement d'oxyde d'aluminium sur des parois d'un conduit interne (1 1 ) de pièce de fonderie (10) en alliage d'aluminium, le procédé comprenant l'insertion d'une cathode (3) dans le conduit (1 1 ), la mise en circulation d'une solution électrolytique dans ledit conduit entre la cathode (3) et les parois du conduit (1 1 ) formant anode, et l'application d'une différence de potentiel entre l'anode et la cathode, 1. A method of forming an aluminum oxide coating on walls of an inner duct (1 1) of an aluminum alloy casting (10), the method comprising inserting a cathode (3) ) in the conduit (1 1), the circulation of an electrolytic solution in said conduit between the cathode (3) and the walls of the duct (1 1) forming anode, and the application of a potential difference between the anode and the cathode,
le procédé étant caractérisé en ce que l'application de la différence de potentiel entre l'anode et la cathode comprend l'application d'une série d'impulsions de tension continue à l'anode. the method being characterized in that the application of the potential difference between the anode and the cathode comprises applying a series of DC voltage pulses to the anode.
2. Procédé de formation selon la revendication 1 , caractérisé en ce que chaque impulsion de la série présente une durée comprise entre 0.01 et 0.02 s et deux impulsions successives sont séparées de 0.001 à 0.01 s. 2. Training method according to claim 1, characterized in that each pulse of the series has a duration between 0.01 and 0.02 s and two successive pulses are separated from 0.001 to 0.01 s.
3. Procédé de formation selon l'une des revendications 1 ou 2, caractérisé en ce que la tension appliquée à l'anode varie lors de la série d'impulsions, et est comprise entre 0 et 150 V pour maintenir une densité de courant comprise entre 10 et 50 A dm2 de surface à traiter. 3. Training method according to one of claims 1 or 2, characterized in that the voltage applied to the anode varies during the series of pulses, and is between 0 and 150 V to maintain a current density included between 10 and 50 A dm 2 of surface to be treated.
4. Procédé de formation selon l'une des revendications 1 à 3, caractérisé en ce que la durée totale de la série d'impulsions est comprise entre 30 et 300 s en fonction du type d'alliage à traiter et de l'épaisseur d'oxyde souhaitée. 4. Formation method according to one of claims 1 to 3, characterized in that the total duration of the series of pulses is between 30 and 300 s depending on the type of alloy to be treated and the thickness of the desired oxide.
5. Procédé de formation selon l'une des revendications 1 à 4, caractérisé en ce que l'électrolyte comprend 10 à 20% d'acide sulfurique et 1 à 5% de sulfate ferreux. 5. Formation process according to one of claims 1 to 4, characterized in that the electrolyte comprises 10 to 20% sulfuric acid and 1 to 5% ferrous sulfate.
6. Procédé de formation selon l'une des revendications 1 à 5, dans lequel le débit d'électrolyte dans un conduit est compris entre 0.5 et 2,0 m3/h par dm2 de surface à traiter. 6. The forming method according to one of claims 1 to 5, wherein the flow of electrolyte in a conduit is between 0.5 and 2.0 m 3 / h per dm 2 of surface to be treated.
7. Procédé de formation selon l'une des revendications 1 à 6 dans lequel la température de l'électrolyte dans un conduit est compris entre -10°C et 0 °C. 7. The forming method according to one of claims 1 to 6 wherein the temperature of the electrolyte in a conduit is between -10 ° C and 0 ° C.
8. Procédé de formation selon l'une des revendications précédentes caractérisé en ce que la cathode (3) est conformée pour épouser la forme du ou des conduits internes (1 1 ) de la pièce de fonderie (10), en laissant un interstice moyen compris entre 3 et 15 mm entre la cathode et la paroi du conduit. 8. Training method according to one of the preceding claims characterized in that the cathode (3) is shaped to conform to the shape of the internal duct (s) (1 1) of the casting (10), leaving an average gap between 3 and 15 mm between the cathode and the duct wall.
9. Culasse automobile (10) en alliage d'aluminium caractérisée en ce qu'elle comprend, sur les parois d'au moins un conduit interne (1 1 ), un revêtement (13) d'oxyde d'aluminium d'une épaisseur comprise entre 50 et 200 μηι, adapté pour assurer l'étanchéité et l'isolation thermique de la paroi du conduit interne de la culasse lors de l'écoulement, dans ledit conduit, de gaz d'échappement à une température supérieure à 900 °C. Automotive cylinder head (10) made of aluminum alloy, characterized in that it comprises, on the walls of at least one inner pipe (1 1), a coating (13) of aluminum oxide of a thickness between 50 and 200 μηι, adapted for sealing and thermal insulation of the wall of the internal duct of the cylinder head during the flow, in said duct, of exhaust gas at a temperature greater than 900 ° C .
10. Culasse automobile (10) selon la revendication 9, la culasse étant obtenue par la mise en œuvre du procédé selon l'une des revendications 1 à 8. 10. Cylinder head (10) according to claim 9, the yoke being obtained by the implementation of the method according to one of claims 1 to 8.
1 1 . Culasse automobile (10) selon l'une des revendications 9 ou 10, dans laquelle les conduits internes (1 1 ) pourvus d'un revêtement (13) d'oxyde sont des conduits d'échappement de produits de combustion. 1 1. The automobile cylinder head (10) according to one of claims 9 or 10, wherein the inner conduits (1 1) provided with a coating (13) of oxide are exhaust pipes of combustion products.
EP16762776.9A 2015-09-03 2016-09-05 Improved method for forming a pipe lining of a cylinder head and cylinder head thus obtained Withdrawn EP3344801A1 (en)

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FR1558180A FR3040712B1 (en) 2015-09-03 2015-09-03 IMPROVED PROCESS FOR FORMING A CYLINDER HEAD CONDUIT COVER AND THUS OBTAINED
PCT/EP2016/070897 WO2017037303A1 (en) 2015-09-03 2016-09-05 Improved method for forming a pipe lining of a cylinder head and cylinder head thus obtained

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CN113294261B (en) * 2021-06-29 2022-08-23 潍柴动力股份有限公司 Cylinder cover, coating preparation device and coating preparation method
CN113441703A (en) * 2021-06-29 2021-09-28 潍柴动力股份有限公司 Preparation method of steel cylinder sleeve and steel cylinder sleeve

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CA2997386A1 (en) 2017-03-09
US20180252180A1 (en) 2018-09-06
WO2017037303A1 (en) 2017-03-09
JP2018527516A (en) 2018-09-20
FR3040712B1 (en) 2019-12-13
FR3040712A1 (en) 2017-03-10

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