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EP2878712A1 - Aluminium-lithium alloy component including a ceramic coating and method for forming the coating - Google Patents

Aluminium-lithium alloy component including a ceramic coating and method for forming the coating Download PDF

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Publication number
EP2878712A1
EP2878712A1 EP14192317.7A EP14192317A EP2878712A1 EP 2878712 A1 EP2878712 A1 EP 2878712A1 EP 14192317 A EP14192317 A EP 14192317A EP 2878712 A1 EP2878712 A1 EP 2878712A1
Authority
EP
European Patent Office
Prior art keywords
component
coating
thickness
voltage
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14192317.7A
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German (de)
French (fr)
Other versions
EP2878712B1 (en
Inventor
Frédéric Dreyer-Gonzales
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.)
Officine Panerai AG
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Officine Panerai AG
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Publication of EP2878712A1 publication Critical patent/EP2878712A1/en
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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
    • C25D11/022—Anodisation on selected surface areas
    • 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
    • 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
    • C25D11/12—Anodising more than once, e.g. in different baths
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
    • 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
    • C25D11/16—Pretreatment, e.g. desmutting
    • 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
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a component comprising an aluminum and lithium alloy coated with a ceramic coating. As well as the process for forming the coating.
  • Aluminum alloys containing lithium have interesting properties. Among them we can mention their lightness compared to other conventional aluminum alloys. Indeed, lithium is the lightest of the metallic elements and, for each 1% of lithium added to the aluminum alloy makes it possible to reduce by 3% the density of the aluminum and to increase by 5% its elastic modulus . This type of alloy also has a high resistance to fatigue and corrosion, thus extending the life of the product. These alloys are 100% recyclable. Aluminum alloys containing lithium find their applications in the fields of aeronautics, aerospace and the military.
  • An object of the present invention is to provide a coated component free from the limitations of known components.
  • a component comprising an aluminum alloy comprising between 0.1 and 10% by weight of lithium, characterized in that said component is treated using a process of oxidation by micro-arc plasma to obtain a ceramic coating on the surface of the aluminum alloy.
  • the invention also relates to a method for growing a ceramic coating on the surface of the component, the process being a plasma micro-arc oxidation process and comprising the steps of immersing the component to be coated in an electrolytic bath composed of an aqueous solution of alkali metal hydroxide, the component forming one of the electrodes; and applying an alternating current having a frequency of between 10 Hz to 10,000 Hz, so as to apply a voltage between the component and another electrode varying between 0 V and a value between 100 V and 1000 V.
  • This solution has the advantage over the prior art of providing a component having a high hardness, excellent resistance to wear, impact, and corrosion.
  • micro-arc plasma The oxidation process by micro-arc plasma is also a technology so the environmental impact is low, especially in view of conventional anodizing techniques so acidic baths are strongly discouraged for the protection of the environment.
  • a component 1 comprises an aluminum alloy comprising between 0.1 and 10% by weight of lithium.
  • the component is treated using a plasma micro-arc oxidation process (also known as “micro-arc oxidation” and acronym “MAO") so as to obtain a ceramic coating 2 on the surface of the aluminum alloy.
  • a plasma micro-arc oxidation process also known as "micro-arc oxidation” and acronym “MAO”
  • the aluminum alloy containing lithium may be one of the commercial alloys available on the market.
  • the aluminum-lithium alloy may include any of the alloys listed in Table 1.
  • the first line gives the name of the alloy and the left column the element as well as the content of the element in% by weight in the successive columns.
  • Such an aluminum-lithium alloy will therefore contain up to 2.45% by weight of lithium, more particularly between 0.88 and 2.45% by weight of lithium.
  • the figure 1 illustrates an arrangement of an installation, in which a tank 3 contains an electrolytic bath 4. Inside the electrolyte 4 plunges a counter-electrode, or cathode, and an anode which corresponds to the component 1 to be coated. To the figure 1 are equally represented a power supply block 6 able to generate an alternating current 31.
  • the micro-arc plasma oxidation process comprises the steps of immersing the component 1 to be coated in the electrolyte 4 and of passing the alternating current 31 so as to apply a voltage between the component 1 and the cathode 5.
  • the electrolyte 4 may comprise an aqueous solution of alkali metal hydroxide, such as potassium or sodium, and an oxyacid salt of an alkali metal.
  • the electrolyte 4 is typically maintained at a temperature between 10 ° C and 55 ° C.
  • the applied current comprises positive and negative current pulses alternating with a frequency of between 10 Hz and 10,000 Hz.
  • the amplitude of the current pulses is between 2 and 200 A / dm 2 so as to apply a voltage between the component 1 and the cathode 5 of the order of 100 V to 1000 V. Indeed, a voltage of 100 and 1000V makes it possible to create an electrolytic plasma necessary for the formation of the coating 2 on the component 1.
  • the current pulses are separated by a dead time where no current is applied.
  • the duration of the dead time is preferably about 10% of the total duration of the current pulse.
  • the duration of the dead time is such that the voltage drops to zero.
  • each of the positive and negative current pulses may have a maximum amplitude followed by a decrease of the current to a zero value.
  • the duration of the pulse where the value of the current is zero is about 10% of the total duration of the current pulse.
  • the voltage must drop to zero, that is to say that the voltage is cycled between a base voltage (baseline) and a ceiling voltage, or ceiling (ceiling line).
  • the minimum base voltage is preferably adjusted to a voltage of between 0 and 99.9% of the maximum peak of the ceiling voltage.
  • the base voltage (for example 30% of the ceiling voltage) will promote the formation of micro-arcs emission visible to the naked eye, while a larger base voltage (for example 60% of the voltage ceiling), will promote the creation of a continuous plasma, also visible to the naked eye (relative to the retinal perception of 0.1 to 0.2 seconds).
  • the influence of the choice of the basic minimum average voltages with respect to the maximum voltage and thus the type of micro-arcs obtained thus makes it possible to master a more or less dense and homogeneous layer.
  • the densification of the layer is also subject to the frequency of alternation between the anode and cathode currents. Indeed in the first case the growth of the nanoporous layer will be realized whereas in the second case the densification of the nanoporosities will operate.
  • the growth rate of the coating 1 depends on the type of frequency and the shape of the pulse, in particular the passage between a cathodic and anodic current (and vice versa) and the current amplitude (and therefore the applied voltage) .
  • the growth rate of the coating is of the order of 1 micron / minute for an applied voltage of 100 to 400 V and a frequency of the order of 1000 Hz.
  • the thickness of the coating thus obtained can range from a few microns, homogeneously on the part, as long as the setting used to maintain the component in the bath is adapted and does not modify the formation of micro arcs and do not extinguish them,) to a few hundred microns.
  • the micro-arc plasma oxidation process is described, for example, in the document WO03 / 083181 .
  • the figure 2 shows a sectional view of the component with the coating 1 formed by the plasma micro-arc oxidation process.
  • the coating comprises a thick functional ceramic layer 21 thick forming about two thirds of the total thickness of the coating 2, and a porous outer layer 22 forming about one third of the total thickness of the coating 2 Moreover, during its growth, the coating 2 is formed in part by the transformation of the substrate material 7 and partly by growth beyond the initial surface 8 of the component (represented by the hatched line in the figure 2 ). In the figure 2 , the excess thickness of the coating 2 is represented by the difference in thickness between the initial surface 8 and the upper surface of the layer 22.
  • the coating 1 formed by the plasma micro-arc oxidation process on the aluminum-lithium alloy component has a high hardness, close to 2000 Hv. It also has excellent resistance to wear, shock, corrosion.
  • the coating 1 is of color corresponding to the natural color of the oxidized aluminum. For example, the coating 1 is dark brown in the case of the aluminum-lithium alloy 2050 (see Table 1).
  • the oxidation process may comprise a preliminary step of preparing the surface 8 of the component 1.
  • This preparation step may comprise the cleaning and degreasing of the surface 8, for example with boiling water or with an alkaline cleaning agent such as a PARCO cleaner solution (product of Henkel Surface Technologies division of Henkel Corporation, Madison Heights, Michigan).
  • the preparation step may be followed by a rinsing step, for example with distilled water.
  • a tribofinishing step can be carried out after the formation of the coating 1 by the oxidation process.
  • This tribofinishing step may include, for example, microsablage.
  • the figure 3 shows a coating 1 formed by the oxidation process of the invention.
  • Figures 3a and 3c show the coating 2 seen from the front, respectively after its formation ( figure 3a ) and after the tribofinition stage ( figure 3c ).
  • the figure 3b is a sectional view showing the Al-Li alloy substrate 7 and the coating 2.
  • the component 1 to be coated may also be derived from a conventional shaping process such as machining, bar turning or setting. form by molding process of liquid aluminum (Cobapress process type).
  • the plasma micro-arc oxidation process has been applied to different parts of a watch case made of an aluminum-lithium alloy.
  • the figure 4 illustrates a perspective of such a watch case 9.
  • the coating 1 has been formed on parts of the watch case 9 comprising a middle part 91, a middle horn 92, a lever 93, a fastening bridge 94 , a bottom (not visible in the figure), a bezel 95 and a crown cover 96.
  • the Figures 5 to 9 show micrographs of views of a metallographic section of the coatings 2 formed by the oxidation process on the different parts of the watch case 9.
  • the figure 5 shows the coating 2 formed on the lever 93.
  • the figure 6 shows the coating 2 formed on the bezel 95.
  • figure 7 shows the coating 2 formed on the middle part 91.
  • the figure 8 shows the coating 2 formed on the middle horn 92.
  • the visible layer in pale gray corresponds to a copper plating layer 10 deposited on the coating for protection purposes during the preparation of the metallographic section.
  • the portion of the component 1 comprises one or more areas having a fine structuring, for example a thread, holes or tappings
  • a fine structuring for example a thread, holes or tappings
  • the coating 2 having a lower thickness than on the rest of the surface of the component 1.
  • the formation of a thick coating in the fine structuring zones can result in a leveling of the structuring. This is particularly the case when the structuring has a dimension smaller than 100 ⁇ m.
  • the oxidation process comprises a step of forming the coating 2 on the zone or zones having fine structuring.
  • the zone or zones with fine structuring are then masked so as to form the coating 2 on the rest of the component 1 without affecting the zone or zones having fine structuring.
  • the coating is formed on the remainder of the surface of the component 1.
  • the thickness of the coating in the area or areas with fine structuring will depend on the size of the patterning.
  • the coating can be formed on the area or areas with fine structuring with a thickness of about 10% of the dimension of the structuring.
  • the area or areas with fine structuring can include threads, holes, tapping, etc.
  • the figure 9 shows a sectional view of a threaded portion of the middle horn 92.
  • the thread has a dimension (distance between the valley and the top) of a few tens of microns.
  • the threaded portion, as well as the rest of the middle horn 92, was first oxidized according to the oxidation process of the invention so as to form the coating 2 (black layer) with a thickness of a few microns (typically between 1 and 5 ⁇ m).
  • the threaded portion was then masked and the rest of the middle horn 92 was again oxidized according to the oxidation process of the invention, making it possible to form the coating 2 with a thickness of several tens to hundreds of microns, such illustrated in figure 8 .
  • the threaded portion being masked during this step, the coating 2 does not believe more in this place and its thickness remains unchanged.
  • the coating 2 having a small thickness in the zone or zones with the fine structuring makes it possible to densify and harden these zones without however leveling the structuring.
  • the masking of the area or zones with fine structuring can be achieved using silicone gaskets or any other protective means resistant to oxidation treatment by micro-arc plasma and can be removed at the end of the process.
  • the graph of the figure 10 relates the measured thicknesses of the coating 2 formed on the different parts of the watch case 9 as discussed above.
  • the bottom line of the graph gives the value of the thickness.
  • the coating 2 with a thickness of 50 ⁇ m is formed on the middle part 91 and the bottom of the box 9.
  • the coating 2 has a thickness of 45 ⁇ m on the fixing bridge 94 and the crown cover 96, ect.
  • Table 2 reports the thickness measured for the coating 2 formed on the various threads present on the watch case 9, for example, in the threaded axis of the middle part 91, for fixing the lever 93 on the fixing bridge 94 for fixing the fixing bridge 94 on the middle part 91.
  • the three lines 1, 2 and 3 in the table 2 correspond to the thickness of the coating 2 measured at the top of three successive threads, as shown in FIG. figure 11 .
  • the graph of the figure 12 summarizes different thickness measurements of the coating 2 at the holes and threads of the various elements of the box 9.
  • the figure 16a shows a photograph of an aluminum-lithium alloy watch case 9 which has undergone the oxidation process of the invention.
  • the figure 16b shows a detail of the housing 9, in particular a portion of the fixing bridge 94, the lever 93 and the bezel 95. photographs allow to assess the surface state of the component with the coating and, in this case, the final step of microsablage.
  • the figure 13 shows the state of the surface of the watchband of lithium aluminum alloy on which the coating was formed by the oxidation process of the invention after 6 hours of wear according to the test above.
  • Fine scratch tests were also carried out.
  • the conditions of these tests included the rotation of the test sample at 90 rpm, in a box with a volume of 0.6 liter with a diameter of 80 mm, height of 60 mm, blotter wall with 5 to 15 markers and 10g of bremor BR 650 glass powder.
  • the duration of the test was 24 hours.
  • the figure 17 shows tables 3 and 4 which represent the observations made for different durations of solicitations from 1 min to 24 hours.
  • the figure 14 shows a photomicrograph of the state of the surface of the middle part after 12 hours of fine scratches. These tests show that the ceramization process also allows excellent scratch resistance.
  • Gravel bed scrap tests were also performed using a test method according to ISO 23160 including falls in a bed of gravel and ceramic chips 8 cm by 500 cm 2 of ceramics 3 mm diameter, with a length of 12 mm and hardness of 900HV ⁇ 100Hv. The height of fall was 40cm.
  • the watch case to be tested is "loaded" with a weight representing the weight of the mechanical movement normally integrated in the watch head. After a dozen falls on a gravel / ceramic bed, there are very slight impacts on the edges, as can be seen in the diagram. figure 14 which shows the surface condition after ten of these tests to falls in gravel bed height 40cm of a weighted middle with a weight representing the weight of the mechanical movement. These tests show that the ceramization process also allows excellent impact and impact resistance 40cm on a gravel / ceramic bed.
  • Synthetic sweat tests were also performed. These tests were carried out according to the conditions of the NIHS 96-50 and ISO 3160-2 standards, in which the tested parts are put on a cotton pad soaked in sweat in an environment of 40 ° C ⁇ 2 ° C humidity 95 to 100 % relative humidity test duration over 6 days.
  • a lithium aluminum provides the following properties: 25% lighter than conventional materials, thus optimizing the design of structural parts and reducing the weight of a watch case, for example, better resistance to fatigue and fatigue. corrosion, which makes the product more reliable and lengthier, 100% recyclable, making a major contribution to a sustainable watch industry.
  • the coating 2 obtained by the process of the invention is advantageous for the components of a mechanical watch subjected to friction or mechanical stress. It is also advantageous for treating watchmaking components, such as the example of the watch case 9 above, which are subject to aggressive environmental constraints such as wear, humidity, salinity (sea, tropical climates or other ). Of course, the component 1 comprising the coating 2 is not only of interest in the watch industry but can also be used in various fields such as eyewear and writing instruments.

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

Abstract

L'invention concerne un composant (1) comprenant un alliage d'aluminium comprenant entre 0.1 et 10 % en poids de lithium, caractérisé en ce ledit composant (1) est traité à l'aide d'un procédé d'oxydation par micro-arc plasma permettant d'obtenir un revêtement céramique (2) à la surface de l'alliage d'aluminium. L'invention concerne également un procédé permettant de croître le revêtement céramique (2) à la surface du composant.The invention relates to a component (1) comprising an aluminum alloy comprising between 0.1 and 10% by weight of lithium, characterized in that said component (1) is treated using a microorganism oxidation process. plasma arc for obtaining a ceramic coating (2) on the surface of the aluminum alloy. The invention also relates to a method for growing the ceramic coating (2) on the surface of the component.

Description

Domaine techniqueTechnical area

La présente invention concerne un composant comprenant un alliage d'aluminium et de lithium revêtu d'un revêtement céramique. Ainsi que le procédé pour former le revêtement.The present invention relates to a component comprising an aluminum and lithium alloy coated with a ceramic coating. As well as the process for forming the coating.

Etat de la techniqueState of the art

Les alliages d'aluminium contenant le lithium possèdent des propriétés intéressantes. Parmi elles on peut mentionner leur légèreté en comparaison aux autres alliages d'aluminium conventionnels. En effet, le lithium est le plus léger des éléments métallique et, pour chaque 1 % de lithium ajouté à l'alliage d'aluminium permet de réduire de 3 % la densité de l'aluminium et d'augmenter de 5% son module élastique. Ce type d'alliage a également une grande résistance à la fatigue et à la corrosion, permettant ainsi d'allonger la durée de vie du produit. Ces alliages sont 100% recyclables. Les alliages d'aluminium contenant le lithium trouvent leurs applications dans les domaines de l'aéronautique, de l'aérospatiale et dans le militaire.Aluminum alloys containing lithium have interesting properties. Among them we can mention their lightness compared to other conventional aluminum alloys. Indeed, lithium is the lightest of the metallic elements and, for each 1% of lithium added to the aluminum alloy makes it possible to reduce by 3% the density of the aluminum and to increase by 5% its elastic modulus . This type of alloy also has a high resistance to fatigue and corrosion, thus extending the life of the product. These alloys are 100% recyclable. Aluminum alloys containing lithium find their applications in the fields of aeronautics, aerospace and the military.

Cependant, ces alliages présentent une mauvaise résistance à l'usure et à la corrosion. En effet, malgré l'ajout de lithium, cet alliage, comme tous les alliages d'aluminium brut, présente des faiblesses à la corrosion et à l'usure et impacts.However, these alloys have poor resistance to wear and corrosion. Indeed, despite the addition of lithium, this alloy, like all raw aluminum alloys, has weaknesses in corrosion and wear and impacts.

Bref résumé de l'inventionBrief summary of the invention

Un but de la présente invention est de proposer un composant revêtu exempt des limitations des composants connus.An object of the present invention is to provide a coated component free from the limitations of known components.

Selon l'invention, ces buts sont atteints notamment au moyen d'un composant comprenant un alliage d'aluminium comprenant entre 0.1 et 10 % en poids de lithium, caractérisé en ce ledit composant est traité à l'aide d'un procédé d'oxydation par micro-arc plasma permettant d'obtenir un revêtement céramique à la surface de l'alliage d'aluminium.According to the invention, these objects are achieved in particular by means of a component comprising an aluminum alloy comprising between 0.1 and 10% by weight of lithium, characterized in that said component is treated using a process of oxidation by micro-arc plasma to obtain a ceramic coating on the surface of the aluminum alloy.

L'invention concerne également un procédé permettant de croître un revêtement céramique à la surface du composant, le procédé étant un procédé d'oxydation par micro-arc plasma et comprenant les étapes d'immerger le composant à revêtir dans un bain électrolytique composé d'une solution aqueuse d'hydroxyde de métal alcalin, le composant formant l'une des électrodes; et d'appliquer un courant alternatif ayant une fréquence comprise entre 10 Hz à 10'000 Hz, de façon à appliquer une tension entre le composant et une autre électrode variant entre 0 V et une valeur comprise entre 100 V et 1000 V.The invention also relates to a method for growing a ceramic coating on the surface of the component, the process being a plasma micro-arc oxidation process and comprising the steps of immersing the component to be coated in an electrolytic bath composed of an aqueous solution of alkali metal hydroxide, the component forming one of the electrodes; and applying an alternating current having a frequency of between 10 Hz to 10,000 Hz, so as to apply a voltage between the component and another electrode varying between 0 V and a value between 100 V and 1000 V.

Cette solution présente notamment l'avantage par rapport à l'art antérieur de fournir un composant ayant une dureté élevée, une excellente résistance à l'usure, aux chocs, et à la corrosion.This solution has the advantage over the prior art of providing a component having a high hardness, excellent resistance to wear, impact, and corrosion.

Le procédé d'oxydation par micro-arc plasma est également une technologie donc l'impact environnemental est faible, en particulier au vu des techniques d'anodisation conventionnelle donc les bains acides sont fortement déconseillés pour la protection de l'environnement.The oxidation process by micro-arc plasma is also a technology so the environmental impact is low, especially in view of conventional anodizing techniques so acidic baths are strongly discouraged for the protection of the environment.

Brève description des figuresBrief description of the figures

Des exemples de mise en oeuvre de l'invention sont indiqués dans la description illustrée par les figures annexées dans lesquelles :

  • la figure 1 illustre une installation d'électrolyse;
  • la figure 2 montre une vue en coupe du composant avec le revêtement formé par le procédé d'oxydation par micro-arc plasma;
  • la figure 3 montre un revêtement formé par le procédé d'oxydation de l'invention;
  • la figure 4 illustre une perspective d'une telle boite de montre;
  • la figure 5 montre le revêtement formé sur un levier;
  • la figure 6 montre le revêtement formé sur une lunette;
  • la figure 7 montre le revêtement formé sur une carrure;
  • la figure 8 montre le revêtement formé sur la corne de carrure;
  • la figure 9 montre un vue en coupe d'une portion filetée de la corne de carrure;
  • la figure 10 est un graphique qui rapporte les épaisseurs mesurée du revêtement formé sur les différentes parties de la boite de montre;
  • la figure 11 montre les endroits de mesure d'épaisseur du revêtement;
  • la figure 12 est un graphique qui rapporte les épaisseurs mesurée du revêtement formé sur les différentes parties de la boite de montre.
  • la figure 13 montre l'état de la surface de la carrure de montre en alliage d'aluminium-lithium sur laquelle le revêtement a été formé, après usure;
  • la figure 14 montre l'état de la surface de la carrure de montre en alliage d'aluminium-lithium sur laquelle le revêtement a été formé, après des tests de chocs;
  • la figure 15 montre l'état de la surface de la carrure de montre en alliage d'aluminium-lithium sur laquelle le revêtement a été formé, après des tests de corrosion; et
  • la figure 16 montre une photographie d'un boîtier de montre en alliage aluminium-lithium ayant subi le procédé d'oxydation de l'invention.
Examples of implementation of the invention are indicated in the description illustrated by the appended figures in which:
  • the figure 1 illustrates an electrolysis plant;
  • the figure 2 shows a sectional view of the component with the coating formed by the plasma micro-arc oxidation process;
  • the figure 3 shows a coating formed by the oxidation process of the invention;
  • the figure 4 illustrates a perspective of such a watch case;
  • the figure 5 shows the coating formed on a lever;
  • the figure 6 shows the coating formed on a telescope;
  • the figure 7 shows the coating formed on a middle part;
  • the figure 8 shows the coating formed on the middle horn;
  • the figure 9 shows a sectional view of a threaded portion of the middle horn;
  • the figure 10 is a graph that reports the measured thicknesses of the coating formed on the different parts of the watch case;
  • the figure 11 shows the places of thickness measurement of the coating;
  • the figure 12 is a graph that reports the measured thicknesses of the coating formed on the different parts of the watch case.
  • the figure 13 shows the condition of the surface of the aluminum-lithium alloy watchband on which the coating was formed, after wear;
  • the figure 14 shows the condition of the surface of the aluminum-lithium alloy watchband on which the coating was formed, after shock tests;
  • the figure 15 shows the condition of the surface of the aluminum-lithium alloy watchband on which the coating was formed, after corrosion tests; and
  • the figure 16 shows a photograph of an aluminum-lithium alloy watch case that has undergone the oxidation process of the invention.

Exemple(s) de mode de réalisation de l'inventionExample (s) of embodiment of the invention

Selon l'invention, un composant 1 comprend un alliage d'aluminium comprenant entre 0.1 et 10 % en poids de lithium. Le composant est traité à l'aide d'un procédé d'oxydation par micro-arc plasma (aussi connu sou le nom anglais de "micro-arc oxydation" et l'acronyme "MAO") de sorte à obtenir un revêtement céramique 2 à la surface de l'alliage d'aluminium.According to the invention, a component 1 comprises an aluminum alloy comprising between 0.1 and 10% by weight of lithium. The component is treated using a plasma micro-arc oxidation process (also known as "micro-arc oxidation" and acronym "MAO") so as to obtain a ceramic coating 2 on the surface of the aluminum alloy.

L'alliage d'aluminium contenant du lithium peut être un des alliages commerciaux disponibles sur le marché. Par exemple, l'alliage d'aluminium-lithium peut comprendre l'un des alliages mentionnés dans la table 1. Dans la table, la première ligne donne le nom de l'alliage et la colonne de gauche l'élément ainsi que le contenu de l'élément en % en poids dans les colonnes successives. Un tel alliage d'aluminium-lithium contiendra donc jusqu'à 2.45 % en poids de lithium, plus particulièrement entre 0.88 et 2.45 % en poids de lithium. Table 1 alliage 2050 2090 2091 2099 2195 2196 2199 8090 Weldalite 049 Cu 4.3 2.7 2.1 2.4-3.0 3.05 2.90 2.3-2.9 1.3 5.4 Li 0.88 2.2 2.0 1.6-2.0 1.70 1.67 1.4-1.8 2.45 1.3 Zn <0.01 - - 0.4-1.0 0.01 0.01 0.2-0.9 - - Mg 0.58 - - 0.1-0.5 0.39 0.40 0.05-0.4 0.95 0.4 Mn - - - 0.1-0.5 0.01 0.31 0.1-0.5 - - Ag 0.34 - - - 0.35 0.38 - - 0.4 Zr 0.13 0.12 0.1 0.05-0.12 0.12 0.1 0.05-0.12 0.12 0.14 Fe 0.03 - - 0.07 max 0.05 0.04 0.07 max - - Si 0.03 - - 0.05 max 0.03 0.03 0.05 max - - Ti 0.04 - - - 0.03 0.03 - - - Al reste reste reste reste reste reste reste reste reste The aluminum alloy containing lithium may be one of the commercial alloys available on the market. For example, the aluminum-lithium alloy may include any of the alloys listed in Table 1. In the table, the first line gives the name of the alloy and the left column the element as well as the content of the element in% by weight in the successive columns. Such an aluminum-lithium alloy will therefore contain up to 2.45% by weight of lithium, more particularly between 0.88 and 2.45% by weight of lithium. Table 1 alloy 2050 2090 2091 2099 2195 2196 2199 8090 Weldalite 049 Cu 4.3 2.7 2.1 2.4-3.0 3.05 2.90 2.3-2.9 1.3 5.4 Li 0.88 2.2 2.0 1.6-2.0 1.70 1.67 1.4-1.8 2.45 1.3 Zn <0.01 - - 0.4-1.0 0.01 0.01 0.2-0.9 - - mg 0.58 - - 0.1-0.5 0.39 0.40 0.05-0.4 0.95 0.4 mn - - - 0.1-0.5 0.01 0.31 0.1-0.5 - - Ag 0.34 - - - 0.35 0.38 - - 0.4 Zr 0.13 0.12 0.1 0.05-0.12 0.12 0.1 0.05-0.12 0.12 0.14 Fe 0.03 - - 0.07 max 0.05 0.04 0.07 max - - Yes 0.03 - - 0.05 max 0.03 0.03 0.05 max - - Ti 0.04 - - - 0.03 0.03 - - - al rest rest rest rest rest rest rest rest rest

La figure 1 illustre un agencement d'une installation, dans laquelle une cuve 3 contient un bain électrolytique 4. A l'intérieur de l'électrolyte 4 plonge une contre-électrode, ou cathode, 5 et une anode qui correspond au composant 1 à revêtir. A la figure 1 sont également représentés un bloc d'alimentation en courant 6 apte à générer un courant alternatif 31.The figure 1 illustrates an arrangement of an installation, in which a tank 3 contains an electrolytic bath 4. Inside the electrolyte 4 plunges a counter-electrode, or cathode, and an anode which corresponds to the component 1 to be coated. To the figure 1 are equally represented a power supply block 6 able to generate an alternating current 31.

Selon un mode de réalisation, le procédé d'oxydation par micro-arc plasma comprend les étapes d'immerger le composant 1 à revêtir dans l'électrolyte 4 et de faire passer le courant alternatif 31 de façon à appliquer une tension entre le composant 1 et la cathode 5.According to one embodiment, the micro-arc plasma oxidation process comprises the steps of immersing the component 1 to be coated in the electrolyte 4 and of passing the alternating current 31 so as to apply a voltage between the component 1 and the cathode 5.

L'électrolyte 4 peut comprendre une solution aqueuse d'hydroxyde de métal alcalin, tel que le potassium ou le sodium, et d'un sel oxyacide d'un métal alcalin. L'électrolyte 4 est typiquement maintenu à une température comprise entre 10°C et 55°C.The electrolyte 4 may comprise an aqueous solution of alkali metal hydroxide, such as potassium or sodium, and an oxyacid salt of an alkali metal. The electrolyte 4 is typically maintained at a temperature between 10 ° C and 55 ° C.

De façon préférée, le courant appliqué comprend des pulses de courant positifs et négatifs alternant avec une fréquence comprise entre 10 Hz à 10'000 Hz. L'amplitude des pulses de courant est comprise entre 2 et 200 A/dm2 de manière à appliquer une tension entre le composant 1 et la cathode 5 de l'ordre de 100 V à 1000 V. En effet, une tension comprise de 100 et 1000V permet de créer un plasma électrolytique nécessaire à la formation du revêtement 2 sur le composant 1.Preferably, the applied current comprises positive and negative current pulses alternating with a frequency of between 10 Hz and 10,000 Hz. The amplitude of the current pulses is between 2 and 200 A / dm 2 so as to apply a voltage between the component 1 and the cathode 5 of the order of 100 V to 1000 V. Indeed, a voltage of 100 and 1000V makes it possible to create an electrolytic plasma necessary for the formation of the coating 2 on the component 1.

Dans un mode de réalisation, les pulses de courants sont séparés par un temps mort où aucun courant n'est appliqué. La durée du temps mort est de préférence d'environ 10% de la durée totale du pulse de courant. La durée du temps mort est telle que la tension chute à zéro. Par exemple, chacun des pulses de courant positif et négatif peut présenter une amplitude maximale suivie d'une décroissance du courant jusqu'à une valeur nulle. La durée du pulse où la valeur du courant est nulle est d'environ 10% de la durée totale du pulse de courant.In one embodiment, the current pulses are separated by a dead time where no current is applied. The duration of the dead time is preferably about 10% of the total duration of the current pulse. The duration of the dead time is such that the voltage drops to zero. For example, each of the positive and negative current pulses may have a maximum amplitude followed by a decrease of the current to a zero value. The duration of the pulse where the value of the current is zero is about 10% of the total duration of the current pulse.

Autrement dit, lors du temps mort la tension doit chuter à zéro, c'est-à-dire que la tension est cyclée entre une tension de base (baseline) et une tension plafond, ou maximale (ceiling line). La tension de base minimale est préférablement ajustée à une tension comprise entre 0 et 99,9% du pic maximum de la tension plafond. La tension de base (par exemple 30% de la tension plafond) permettra de favoriser la formation d'émission de micro arcs électriques visible à l'oeil nu, alors qu'une tension de base plus conséquente (par exemple 60% de la tension plafond), permettra de favoriser la création d'un plasma continu, également visible à l'oeil nu (relatif à la perception rétinienne de 0.1 à 0.2 secondes). L'influence du choix des tensions moyennes minimales de base par rapport à la tension maximale et donc du type de micro-arcs obtenus permet donc de maitriser une couche plus ou moins dense et homogène. La densification de la couche étant également sujette à la fréquence d'alternance entre les courants anodiques et cathodiques. En effet dans le premier cas la croissance de la couche nanoporeuse se réalisera alors que dans le second la densification des nanoporosités opérera.In other words, during the dead time the voltage must drop to zero, that is to say that the voltage is cycled between a base voltage (baseline) and a ceiling voltage, or ceiling (ceiling line). The minimum base voltage is preferably adjusted to a voltage of between 0 and 99.9% of the maximum peak of the ceiling voltage. The base voltage (for example 30% of the ceiling voltage) will promote the formation of micro-arcs emission visible to the naked eye, while a larger base voltage (for example 60% of the voltage ceiling), will promote the creation of a continuous plasma, also visible to the naked eye (relative to the retinal perception of 0.1 to 0.2 seconds). The influence of the choice of the basic minimum average voltages with respect to the maximum voltage and thus the type of micro-arcs obtained thus makes it possible to master a more or less dense and homogeneous layer. The densification of the layer is also subject to the frequency of alternation between the anode and cathode currents. Indeed in the first case the growth of the nanoporous layer will be realized whereas in the second case the densification of the nanoporosities will operate.

La vitesse de croissance du revêtement 1 dépend du type de fréquence et de la forme du pulse, en particulier du passage entre un courant cathodique et anodique (et vice-versa) et de l'amplitude de courant (et donc de la tension appliquée). Par exemple, la vitesse de croissance du revêtement est de l'ordre de 1 micron/ minute pour une tension appliquée de 100 à 400 V et une fréquence de l'ordre de 1000 Hz.. L'épaisseur du revêtement ainsi obtenu peut aller de quelques microns, de manière homogène sur la pièce, pour autant que le posage utilisé pour maintenir le composant dans le bain soit adapté et ne modifie pas la formation des micro arcs et ne les éteignent pas,) à quelques centaines de microns. Le procédé d'oxydation par micro-arc plasma est décrit, par exemple, dans le document WO03/083181 .The growth rate of the coating 1 depends on the type of frequency and the shape of the pulse, in particular the passage between a cathodic and anodic current (and vice versa) and the current amplitude (and therefore the applied voltage) . For example, the growth rate of the coating is of the order of 1 micron / minute for an applied voltage of 100 to 400 V and a frequency of the order of 1000 Hz. The thickness of the coating thus obtained can range from a few microns, homogeneously on the part, as long as the setting used to maintain the component in the bath is adapted and does not modify the formation of micro arcs and do not extinguish them,) to a few hundred microns. The micro-arc plasma oxidation process is described, for example, in the document WO03 / 083181 .

La figure 2 montre une vue en coupe du composant avec le revêtement 1 formé par le procédé d'oxydation par micro-arc plasma. Le revêtement comprend une couche dure céramique fonctionnelle 21 épaisse formant environ deux tiers de l'épaisseur totale du revêtement 2, et une couche externe poreuse 22 formant environ un tiers de l'épaisseur totale du revêtement 2 De plus, lors de sa croissance, le revêtement 2 est formé en partie par la transformation de la matière substrat 7 et en partie par croissance au-delà de la surface initiale 8 du composant (représenté par la ligne hachurée dans la figure 2). Dans la figure 2, la surépaisseur du revêtement 2 est représentée par la différence d'épaisseur entre la surface initiale 8 et la surface supérieure de la couche 22.The figure 2 shows a sectional view of the component with the coating 1 formed by the plasma micro-arc oxidation process. The coating comprises a thick functional ceramic layer 21 thick forming about two thirds of the total thickness of the coating 2, and a porous outer layer 22 forming about one third of the total thickness of the coating 2 Moreover, during its growth, the coating 2 is formed in part by the transformation of the substrate material 7 and partly by growth beyond the initial surface 8 of the component (represented by the hatched line in the figure 2 ). In the figure 2 , the excess thickness of the coating 2 is represented by the difference in thickness between the initial surface 8 and the upper surface of the layer 22.

Le revêtement 1 formé par le procédé d'oxydation par micro-arc plasma sur le composant en alliage aluminium-lithium a une dureté élevée, proche de 2000 Hv. Il a également une excellente résistance à l'usure, aux chocs, à la corrosion. Le revêtement 1 est de coloration correspondant à la coloration naturelle de l'aluminium oxydé. Par exemple, le revêtement 1 a une coloration brun foncée dans le cas de l'alliage aluminium-lithium 2050 (voir table 1).The coating 1 formed by the plasma micro-arc oxidation process on the aluminum-lithium alloy component has a high hardness, close to 2000 Hv. It also has excellent resistance to wear, shock, corrosion. The coating 1 is of color corresponding to the natural color of the oxidized aluminum. For example, the coating 1 is dark brown in the case of the aluminum-lithium alloy 2050 (see Table 1).

Le procédé d'oxydation peut comporter une étape préalable de préparation de la surface 8 du composant 1. Cette étape de préparation peut comprendre le nettoyage et dégraissage de la surface 8, par exemple à l'eau bouillante ou à un nettoyant alcalin tel qu'une solution de nettoyant PARCO (produit de Henkel Surface Technologies division de Henkel Corporation, Madison Heights, Michigan). L'étape de préparation peut être suivie d'une étape de rinçage, par exemple à l'eau distillée.The oxidation process may comprise a preliminary step of preparing the surface 8 of the component 1. This preparation step may comprise the cleaning and degreasing of the surface 8, for example with boiling water or with an alkaline cleaning agent such as a PARCO cleaner solution (product of Henkel Surface Technologies division of Henkel Corporation, Madison Heights, Michigan). The preparation step may be followed by a rinsing step, for example with distilled water.

Afin d'obtenir un état de surface optimum et retirer les derniers microns de la couche poreuse 22 de céramique, une étape de tribofinition peut être réalisée à l'issue de la formation du revêtement 1 par le procédé d'oxydation. Cette étape de tribofinition peut comprendre, par exemple, un microsablage.In order to obtain an optimum surface state and remove the last microns of the porous ceramic layer 22, a tribofinishing step can be carried out after the formation of the coating 1 by the oxidation process. This tribofinishing step may include, for example, microsablage.

La figure 3 montre un revêtement 1 formé par le procédé d'oxydation de l'invention. En particulier, les figures 3a et 3c montrent le revêtement 2 vu de face, respectivement après sa formation (figure 3a) et après l'étape de tribofinition (figure 3c). La figure 3b est une vue en coupe montrant le substrat d'alliage Al-Li 7 et du revêtement 2.The figure 3 shows a coating 1 formed by the oxidation process of the invention. In particular, Figures 3a and 3c show the coating 2 seen from the front, respectively after its formation ( figure 3a ) and after the tribofinition stage ( figure 3c ). The figure 3b is a sectional view showing the Al-Li alloy substrate 7 and the coating 2.

Le composant 1 à revêtir peut aussi bien être issu d'un procédé de mise en forme conventionnel de type usinage, décolletage ou mise en forme par procédé de moulage de l'aluminium liquide (type procédé Cobapress).The component 1 to be coated may also be derived from a conventional shaping process such as machining, bar turning or setting. form by molding process of liquid aluminum (Cobapress process type).

A titre d'exemple, le procédé d'oxydation par micro-arc plasma a été appliqué à différentes parties d'une boite de montre fabriqué dans un alliage aluminium-lithium. La figure 4 illustre une perspective d'une telle boite de montre 9. En particulier, le revêtement 1 a été formé sur des parties de la boite de montre 9 comprenant une carrure 91, une corne de carrure 92, un levier 93, un pont de fixation 94, un fond (non visible sur la figure), une lunette 95 et un cache-couronne 96.By way of example, the plasma micro-arc oxidation process has been applied to different parts of a watch case made of an aluminum-lithium alloy. The figure 4 illustrates a perspective of such a watch case 9. In particular, the coating 1 has been formed on parts of the watch case 9 comprising a middle part 91, a middle horn 92, a lever 93, a fastening bridge 94 , a bottom (not visible in the figure), a bezel 95 and a crown cover 96.

Les figures 5 à 9 montrent des micrographies de vues d'une coupe métallographique des revêtements 2 formés par le procédé d'oxydation sur les différentes parties de la boite de montre 9. En particulier, la figure 5 montre le revêtement 2 formé sur le levier 93. La figure 6 montre le revêtement 2 formé sur la lunette 95. La figure 7 montre le revêtement 2 formé sur la carrure 91. La figure 8 montre le revêtement 2 formé sur la corne de carrure 92. Dans ces figures, la couche visible en gris pâle correspond à une couche de cuivrage 10 déposée sur le revêtement à des fins de protection lors de la préparation de la coupe métallographique.The Figures 5 to 9 show micrographs of views of a metallographic section of the coatings 2 formed by the oxidation process on the different parts of the watch case 9. In particular, the figure 5 shows the coating 2 formed on the lever 93. The figure 6 shows the coating 2 formed on the bezel 95. figure 7 shows the coating 2 formed on the middle part 91. The figure 8 shows the coating 2 formed on the middle horn 92. In these figures, the visible layer in pale gray corresponds to a copper plating layer 10 deposited on the coating for protection purposes during the preparation of the metallographic section.

Dans le cas où la portion du composant 1 comprend une ou des zones comportant une structuration fine, par exemple un filetage, des trous ou des taraudages, il peut être avantageux que ces zones soient revêtues avec le revêtement 2 présentant une épaisseur plus faible que sur le reste de la surface du composant 1. En effet, la formation d'un revêtement épais dans les zones structuration fine peut résulter dans un nivellement de la structuration. Ceci est particulièrement le cas lorsque la structuration a une dimension inférieure à 100 µm.In the case where the portion of the component 1 comprises one or more areas having a fine structuring, for example a thread, holes or tappings, it may be advantageous for these areas to be coated with the coating 2 having a lower thickness than on the rest of the surface of the component 1. Indeed, the formation of a thick coating in the fine structuring zones can result in a leveling of the structuring. This is particularly the case when the structuring has a dimension smaller than 100 μm.

Dans un mode de réalisation, le procédé d'oxydation comprend une étape de former le revêtement 2 sur la ou les zones ayant la structuration fine. La ou les zones avec la structuration fine sont ensuite masquées de façon à pouvoir former le revêtement 2 sur le reste du composant 1 sans affecter la ou les zones ayant la structuration fine. Ensuite, le revêtement est formé sur le reste de la surface du composant 1. L'épaisseur du revêtement dans la ou les zones avec la structuration fine dépendra de la dimension de la structuration. Par exemple, le revêtement peut être formé sur la ou les zones avec la structuration fine avec une épaisseur d'environ 10% de la dimension de la structuration.In one embodiment, the oxidation process comprises a step of forming the coating 2 on the zone or zones having fine structuring. The zone or zones with fine structuring are then masked so as to form the coating 2 on the rest of the component 1 without affecting the zone or zones having fine structuring. Then, the coating is formed on the remainder of the surface of the component 1. The thickness of the coating in the area or areas with fine structuring will depend on the size of the patterning. For example, the coating can be formed on the area or areas with fine structuring with a thickness of about 10% of the dimension of the structuring.

Dans le cas de l'exemple de la boite de montre 9 ci-dessus, la ou les zones avec la structuration fine peut comprendre des filetages, trous, taraudage, etc. La figure 9 montre un vue en coupe d'une portion filetée de la corne de carrure 92. Le filetage a une dimension (distance entre la vallée et le sommet) de quelques dizaines de microns. La portion filetée, ainsi que le reste de la corne de carrure 92, a d'abord été oxydée suivant le procédé d'oxydation de l'invention de manière à former le revêtement 2 (couche noire) avec une épaisseur de quelques microns (typiquement entre 1 et 5 µm). La portion filetée a ensuite été masquée et le reste de la corne de carrure 92 a été de nouveau oxydée selon le procédé d'oxydation de l'invention, permettant de former le revêtement 2 avec une épaisseur de plusieurs dizaines à centaines de microns, tel qu'illustré à la figure 8. La portion filetée étant masquée pendant cette étape, le revêtement 2 ne croit pas d'avantage à cet endroit et son épaisseur reste inchangée. Le revêtement 2 ayant une faible épaisseur dans la ou les zones avec la structuration fine permet de densifier et de durcir ces zones sans toutefois niveler la structuration.In the case of the example of the watch case 9 above, the area or areas with fine structuring can include threads, holes, tapping, etc. The figure 9 shows a sectional view of a threaded portion of the middle horn 92. The thread has a dimension (distance between the valley and the top) of a few tens of microns. The threaded portion, as well as the rest of the middle horn 92, was first oxidized according to the oxidation process of the invention so as to form the coating 2 (black layer) with a thickness of a few microns (typically between 1 and 5 μm). The threaded portion was then masked and the rest of the middle horn 92 was again oxidized according to the oxidation process of the invention, making it possible to form the coating 2 with a thickness of several tens to hundreds of microns, such illustrated in figure 8 . The threaded portion being masked during this step, the coating 2 does not believe more in this place and its thickness remains unchanged. The coating 2 having a small thickness in the zone or zones with the fine structuring makes it possible to densify and harden these zones without however leveling the structuring.

Le masquage de la ou les zones avec la structuration fine peut être réalisé à l'aide de joints en silicone ou tout autre moyen de protection résistant au traitement d'oxydation par micro-arc plasma et pouvant être éliminé à la fin du procédé.The masking of the area or zones with fine structuring can be achieved using silicone gaskets or any other protective means resistant to oxidation treatment by micro-arc plasma and can be removed at the end of the process.

Le graphique de la figure 10 rapporte les épaisseurs mesurée du revêtement 2 formé sur les différentes parties de la boite de montre 9 tel que discuté ci-dessus. La ligne du bas du graphique donne la valeur de l'épaisseur. Par exemple, le revêtement 2 d'épaisseur de 50 µm est formé sur la carrure 91 et le fond de la boîte 9. Le revêtement 2 a une épaisseur de 45 µm sur le pont de fixation 94 et le cache-couronne 96, ect.The graph of the figure 10 relates the measured thicknesses of the coating 2 formed on the different parts of the watch case 9 as discussed above. The bottom line of the graph gives the value of the thickness. For example, the coating 2 with a thickness of 50 μm is formed on the middle part 91 and the bottom of the box 9. The coating 2 has a thickness of 45 μm on the fixing bridge 94 and the crown cover 96, ect.

La table 2 rapporte l'épaisseur mesurée pour le revêtement 2 formé sur les différents filetages présents sur la boîte de montre 9, par exemple, dans l'axe fileté de la carrure 91, pour la fixation du levier 93 sur le pont de fixation 94, pour la fixation du pont de fixation 94 sur la carrure 91. Les trois lignes 1, 2 et 3 dans la table 2 correspondent à l'épaisseur du revêtement 2 mesurée au sommet de trois filets successifs, comme montré à la figure 11.

Figure imgb0001
Table 2 reports the thickness measured for the coating 2 formed on the various threads present on the watch case 9, for example, in the threaded axis of the middle part 91, for fixing the lever 93 on the fixing bridge 94 for fixing the fixing bridge 94 on the middle part 91. The three lines 1, 2 and 3 in the table 2 correspond to the thickness of the coating 2 measured at the top of three successive threads, as shown in FIG. figure 11 .
Figure imgb0001

Le graphique de la figure 12 résume différentes mesures d'épaisseur du revêtement 2 au niveau de trous et filetage des différents éléments de la boîte 9.The graph of the figure 12 summarizes different thickness measurements of the coating 2 at the holes and threads of the various elements of the box 9.

La figure 16a montre une photographie d'un boîtier de montre 9 en alliage aluminium-lithium ayant subi le procédé d'oxydation de l'invention. La figure 16b montre un détail du boîtier 9, en particulier une portion du pont de fixation 94, du levier 93 et de la lunette 95. Ces photographies permettent d'apprécier l'état de surface du composant avec le revêtement et, dans ce cas, l'étape finale de microsablage.The figure 16a shows a photograph of an aluminum-lithium alloy watch case 9 which has undergone the oxidation process of the invention. The figure 16b shows a detail of the housing 9, in particular a portion of the fixing bridge 94, the lever 93 and the bezel 95. photographs allow to assess the surface state of the component with the coating and, in this case, the final step of microsablage.

Des tests à l'usure réalisés dans des conditions d'usure de billes à une vitesse de 46 tr/min et avec un mélange de 2 kg de billes céramiques d'un diamètre de 3 mm dans un-demi litre d'eau et 10 cc de mouillant. La durée du test a été de 36 heures. Après 6h de ce test, un brillantage de la surface est observé. Après 36 heures de ce test, aucune évolution ultérieure n'a été observée. Le procédé de céramisation permet donc une excellente résistance à l'usure. L'état de la surface après usure du revêtement de céramisation sur un aluminium lithium est montré à la figure 11 dans le cas d'une surface initiale non usée et après 6h du test, 12h du test et 36h du test.Wear tests carried out under conditions of wear of balls at a speed of 46 rpm and with a mixture of 2 kg of ceramic beads with a diameter of 3 mm in one-half liter of water and cc of wetting. The duration of the test was 36 hours. After 6 hours of this test, a brightening of the surface is observed. After 36 hours of this test, no further evolution was observed. The ceramization process therefore provides excellent wear resistance. The state of the surface after wear of the ceramization coating on a lithium aluminum is shown in FIG. figure 11 in the case of an initial unworn surface and after 6h of the test, 12h of the test and 36h of the test.

La figure 13 montre l'état de la surface de la carrure de montre en alliage d'aluminium lithium sur laquelle le revêtement a été formé par le procédé d'oxydation de l'invention, après 6h d'usure selon le test ci-dessus.The figure 13 shows the state of the surface of the watchband of lithium aluminum alloy on which the coating was formed by the oxidation process of the invention after 6 hours of wear according to the test above.

Des tests de rayures fines ont également été réalisés. Les conditions de ces tests comprenaient la rotation de l'échantillon à tester à 90 tr/min, dans une boite d'un volume de 0.6 litre d'un diamètre de 80mm, hauteur de 60mm, paroi en buvard avec 5 à 15 feutres et 10g de poudre de verre « bremor BR 650 ». La durée du test était de 24 heures. La figure 17 montre les tables 3 et 4 qui représentent les observations faites pour différentes durées de sollicitations de 1 min à 24 heures.Fine scratch tests were also carried out. The conditions of these tests included the rotation of the test sample at 90 rpm, in a box with a volume of 0.6 liter with a diameter of 80 mm, height of 60 mm, blotter wall with 5 to 15 markers and 10g of bremor BR 650 glass powder. The duration of the test was 24 hours. The figure 17 shows tables 3 and 4 which represent the observations made for different durations of solicitations from 1 min to 24 hours.

La figure 14 montre une microphotographie de l'état de la surface de la carrure après 12h de rayures fines. Ces tests montrent que le procédé de céramisation permet également une excellente résistance aux rayures.The figure 14 shows a photomicrograph of the state of the surface of the middle part after 12 hours of fine scratches. These tests show that the ceramization process also allows excellent scratch resistance.

Des tests de chutes dans lit de gravier ont également été réalisés à l'aide d'une méthode de tests selon la norme ISO 23160 comprenant des chutes dans un lit de gravier et chips céramiques de 8 cm sur 500 cm2 de berlingots céramiques de diamètre 3 mm, d'une longueur de 12 mm et de dureté de 900HV ±100Hv. La hauteur de chute était de 40cm.Gravel bed scrap tests were also performed using a test method according to ISO 23160 including falls in a bed of gravel and ceramic chips 8 cm by 500 cm 2 of ceramics 3 mm diameter, with a length of 12 mm and hardness of 900HV ± 100Hv. The height of fall was 40cm.

La boite de montre à tester est « chargée » avec une masselotte représentant le poids du mouvement mécanique normalement intégré dans la tête de montre. On observe après une dizaine de chutes sur lit de gravier/céramique de très faibles impacts aux niveaux des arêtes, tels que visibles dans la figure 14 qui montre l'état de surface après dix de ces tests aux chutes dans lit de gravier hauteur 40cm d'une carrure lestée avec une masselotte représentant le poids du mouvement mécanique. Ces tests montrent que le procédé de céramisation permet également une excellente résistance aux chocs et impacts 40cm sur lit gravier/céramique.The watch case to be tested is "loaded" with a weight representing the weight of the mechanical movement normally integrated in the watch head. After a dozen falls on a gravel / ceramic bed, there are very slight impacts on the edges, as can be seen in the diagram. figure 14 which shows the surface condition after ten of these tests to falls in gravel bed height 40cm of a weighted middle with a weight representing the weight of the mechanical movement. These tests show that the ceramization process also allows excellent impact and impact resistance 40cm on a gravel / ceramic bed.

Des tests de sueur synthétique ont également été réalisés. Ces tests ont été réalisés selon les conditions des normes NIHS 96-50 et ISO 3160-2, dans lesquelles les pièces testées sont mises sur un support de coton imbibé de sueur dans un environnement de 40°C±2°C humidité 95 à 100% humidité relative durée du test sur 6 jours.Synthetic sweat tests were also performed. These tests were carried out according to the conditions of the NIHS 96-50 and ISO 3160-2 standards, in which the tested parts are put on a cotton pad soaked in sweat in an environment of 40 ° C ± 2 ° C humidity 95 to 100 % relative humidity test duration over 6 days.

Après 6 jours, des piqures de corrosion apparaissent sur des zones de mise à nu de l'aluminium. La couche de céramisation permet de créer une couche de protection de l'aluminium substrat (voir la figure 15). Ces tests montrent que le procédé de céramisation permet également une excellente tenue à la corrosion.After 6 days, corrosion pits appear on areas of bare aluminum. The ceramizing layer makes it possible to create a protective layer of the aluminum substrate (see figure 15 ). These tests show that the ceramization process also allows an excellent resistance to corrosion.

Globalement un aluminium lithium apporte les propriétés suivantes : 25% plus légère que les matériaux conventionnels, permettant ainsi d'optimiser la conception des pièces structurelles et de réduire le poids d'une boite de montre, par exemple, Meilleure résistance à la fatigue et à la corrosion, ce qui permet de fiabiliser et d'allonger la durée de vie du produit, 100% recyclable, ce qui apporte une contribution majeure à une industrie horlogère durable.Overall, a lithium aluminum provides the following properties: 25% lighter than conventional materials, thus optimizing the design of structural parts and reducing the weight of a watch case, for example, better resistance to fatigue and fatigue. corrosion, which makes the product more reliable and lengthier, 100% recyclable, making a major contribution to a sustainable watch industry.

Le revêtement 2 obtenu par le procédé de l'invention est avantageux pour les composants d'une montre mécanique soumis à des frottements ou contraintes mécaniques. Il est également avantageux pour traiter des composant d'habillage horloger, comme l'exemple de la boîte de montre 9 ci-dessus, qui sont soumis à des contraintes environnementales agressives type usure, humidité, taux de salinité (mer, climats tropicaux ou autres). Bien sûr, le composant 1 comprenant le revêtement 2 n'est pas seulement d'intérêt dans l'horlogerie mais peut également être également utilisé dans des domaines divers tels que la lunetterie et les instruments d'écritures.The coating 2 obtained by the process of the invention is advantageous for the components of a mechanical watch subjected to friction or mechanical stress. It is also advantageous for treating watchmaking components, such as the example of the watch case 9 above, which are subject to aggressive environmental constraints such as wear, humidity, salinity (sea, tropical climates or other ). Of course, the component 1 comprising the coating 2 is not only of interest in the watch industry but can also be used in various fields such as eyewear and writing instruments.

Numéros de référence employés sur les figuresReference numbers used in the figures

11
composantcomponent
22
revêtementcoating
2121
couche durehard layer
2222
seconde portionsecond portion
33
cuvetank
3131
courant alternatifalternating current
44
bain électrolytiqueelectrolytic bath
55
cathodecathode
66
bloc d'alimentation en courantpower supply
77
substrat d'aluminium-lithiumaluminum-lithium substrate
88
surface initialeinitial surface
99
boite de montrewatch box
9191
carrureshoulders
9292
corne de carrurehorn of middle
9393
levierthe sink
9494
pont de fixationfixing bridge
9595
lunetteglasses
9696
cache-couronnecover ring
1010
couche de cuivragecopper plating

Claims (15)

Composant (1) comprenant un alliage d'aluminium
comprenant entre 0.1 et 10 % en poids de lithium, caractérisé en ce ledit composant (1) est traité à l'aide d'un procédé d'oxydation par micro-arc plasma permettant d'obtenir un revêtement céramique (2) à la surface de l'alliage d'aluminium.Component (1) comprising an aluminum alloy
comprising between 0.1 and 10% by weight of lithium, characterized in that said component (1) is treated using a plasma micro-arc oxidation process to obtain a ceramic coating (2) on the surface aluminum alloy. Le composant selon la revendication 1,
dans lequel le revêtement (2) a une épaisseur comprise entre 1 µm et 100 µm.The component of claim 1,
wherein the coating (2) has a thickness of between 1 μm and 100 μm. Le composant selon la revendication 2,
comprenant au moins une portion comportant une structuration de surface ayant une dimension inférieure à 100 µm; et
dans lequel le revêtement a une épaisseur comprise entre 1 µm et 5 µm.The component of claim 2,
comprising at least one portion having a surface pattern having a size smaller than 100 μm; and
wherein the coating has a thickness of between 1 μm and 5 μm. Le composant selon la revendication 3,
dans lequel le revêtement a une épaisseur comprise entre 5 µm et 100 µm sur le reste du composant, et de préférence entre 20 µm et 50 µm sur le reste du composant.The component of claim 3,
wherein the coating has a thickness of between 5 μm and 100 μm on the rest of the component, and preferably between 20 μm and 50 μm on the rest of the component. Le composant selon l'une des revendications 1 à 4,
comprenant entre 0.88 et 2.45 % en poids de lithium.The component according to one of claims 1 to 4,
comprising between 0.88 and 2.45% by weight of lithium. Le composant selon l'une des revendications 1 à 5,
dans lequel le revêtement a une dureté comprise entre 1800 et 2000 Hv.The component according to one of claims 1 to 5,
wherein the coating has a hardness of between 1800 and 2000 Hv. Le composant selon l'une des revendications 1 à 6,
dans lequel le revêtement est intact après un essai de dix chutes dans lit de gravier à une hauteur de 40 cm du composant, selon la norme ISO 23160.The component according to one of claims 1 to 6,
in which the coating is intact after a trial of ten falls in gravel bed at a height of 40 cm of the component, according to ISO 23160. Le composant selon l'une des revendications 1 à 7,
dans lequel le revêtement montre un état de surface comporte de légères altérations (indice 4) après 36 heures d'un test selon la norme ISO 23160.The component according to one of claims 1 to 7,
in which the coating shows a surface condition has slight alterations (index 4) after 36 hours of a test according to ISO 23160. Le composant selon l'une des revendications 1 à 8, étant un composant horloger, notamment un composant d'habillage ou un composant d'un mouvement, un composant pour la lunetterie ou un composant pour un instrument d'écriture.The component according to one of claims 1 to 8, being a watch component, in particular a dressing component or a component of a movement, a component for eyewear or a component for a writing instrument. Procédé permettant de croître un revêtement céramique (2) à la surface d'un composant comprenant un alliage d'aluminium comprenant entre 0.1 et 10 % en poids de lithium, caractérisé en ce le procédé est un procédé d'oxydation par micro-arc plasma et comprend: immerger le composant à revêtir dans un bain électrolytique (3) composé d'une solution aqueuse d'hydroxyde de métal alcalin, le composant formant l'une des électrodes; appliquer un courant alternatif ayant une fréquence comprise entre 10 Hz à 10'000 Hz, de façon à appliquer une tension entre le composant et une autre électrode variant entre 0 V et une valeur comprise entre 100 V et 1000 V. A process for growing a ceramic coating (2) on the surface of a component comprising an aluminum alloy comprising between 0.1 and 10% by weight of lithium, characterized in that the process is a plasma micro-arc oxidation process and includes: immersing the component to be coated in an electrolytic bath (3) composed of an aqueous solution of alkali metal hydroxide, the component forming one of the electrodes; applying an alternating current having a frequency between 10 Hz and 10,000 Hz, so as to apply a voltage between the component and another electrode varying between 0 V and a value between 100 V and 1000 V. Le procédé selon la revendication 10,
dans lequel la durée du pulse de courant donnant une tension de 0 V est de 10% de la durée totale du pulse donnant une tension comprise entre 100 V et 1000 V.The process according to claim 10,
in which the duration of the current pulse giving a voltage of 0 V is 10% of the total pulse duration giving a voltage of between 100 V and 1000 V. Le procédé selon la revendication 10 ou 11,
dans lequel la tension moyenne minimale est ajustée de façon à être comprise entre 0 et 99,9% de la tension maximale et de préférence entre 30 % et 60% de la tension maximale.The process according to claim 10 or 11,
wherein the minimum average voltage is adjusted to be between 0 and 99.9% of the maximum voltage and preferably between 30% and 60% of the maximum voltage. Le procédé selon l'une des revendications 10 à 12,
dans lequel une zone du composant (1) comporte une structuration fine ayant une dimension inférieure à 100 µm; et dans lequel le procédé comprend en outre: croître le revêtement (2) avec une épaisseur comprise entre 1 µm et 5 µm; masquer ladite zone de sorte que l'application subséquente du procédé n'ait pas d'effet sur ladite zone; et croître le revêtement (2) ayant une épaisseur comprise entre 5 µm et 100 µm sur le reste de la surface du composant (2). The process according to one of claims 10 to 12,
wherein an area of the component (1) has a fine structuring having a size less than 100 μm; and wherein the method further comprises: growing the coating (2) with a thickness of between 1 μm and 5 μm; mask said zone so that the subsequent application of the method has no effect on said zone; and growing the coating (2) having a thickness of between 5 μm and 100 μm on the rest of the surface of the component (2). Le procédé selon l'une des revendications 10 à 13,
comportant en outre une préparation de surface comprenant une étape de nettoyage et dégraissage.The process according to one of claims 10 to 13,
further comprising a surface preparation comprising a cleaning and degreasing step. Le procédé selon l'une des revendications 10 à 14,
comportant en outre une étape de microsablage.The process according to one of claims 10 to 14,
further comprising a microsablage step.
EP14192317.7A 2013-11-11 2014-11-07 Aluminium-lithium alloy component including a ceramic coating and method for forming the coating Active EP2878712B1 (en)

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