EP2878712A1 - Bauteil aus Aluminium-Lithium-Legierung, das eine keramische Ummantelung umfasst, und Verfahren zur Herstellung dieser Ummantelung - Google Patents

Bauteil aus Aluminium-Lithium-Legierung, das eine keramische Ummantelung umfasst, und Verfahren zur Herstellung dieser Ummantelung 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
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EP
European Patent Office
Prior art keywords
component
coating
thickness
voltage
lithium
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Granted
Application number
EP14192317.7A
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English (en)
French (fr)
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EP2878712B1 (de
Inventor
Frédéric Dreyer-Gonzales
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Officine Panerai AG
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Officine Panerai AG
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Publication of EP2878712A1 publication Critical patent/EP2878712A1/de
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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP14192317.7A 2013-11-11 2014-11-07 Bauteil aus Aluminium-Lithium-Legierung, das eine keramische Ummantelung umfasst, und Verfahren zur Herstellung dieser Ummantelung Active EP2878712B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH01881/13A CH708829A1 (fr) 2013-11-11 2013-11-11 Composant en alliage aluminium-lithium comprenant un revêtement céramique et procédé pour former le revêtement.

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EP2878712A1 true EP2878712A1 (de) 2015-06-03
EP2878712B1 EP2878712B1 (de) 2020-05-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876811A (zh) * 2020-07-27 2020-11-03 上海交通大学 一种铝锂合金微弧氧化方法及其采用的电解液

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998358A (en) * 1957-10-02 1961-08-29 Nippon Light Metal Co Method of forming a colored film on an aluminum alloy
WO2003083181A2 (en) 2002-03-27 2003-10-09 Isle Coat Limited Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process
GB2421959A (en) * 2005-01-10 2006-07-12 Short Brothers Plc Anodising aluminium alloy
US20060207884A1 (en) * 2005-03-17 2006-09-21 Volodymyr Shpakovsky Method of producing corundum layer on metal parts
EP1818428A1 (de) * 2004-11-05 2007-08-15 Nihon Parkerizing Co., Ltd. Verfahren zur elektrolytischen keramikbeschichtung für metall, elektrolyt zur verwendung bei der elektrolytischen keramikbeschichtung für metall und metallmaterial

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998358A (en) * 1957-10-02 1961-08-29 Nippon Light Metal Co Method of forming a colored film on an aluminum alloy
WO2003083181A2 (en) 2002-03-27 2003-10-09 Isle Coat Limited Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process
EP1818428A1 (de) * 2004-11-05 2007-08-15 Nihon Parkerizing Co., Ltd. Verfahren zur elektrolytischen keramikbeschichtung für metall, elektrolyt zur verwendung bei der elektrolytischen keramikbeschichtung für metall und metallmaterial
GB2421959A (en) * 2005-01-10 2006-07-12 Short Brothers Plc Anodising aluminium alloy
US20060207884A1 (en) * 2005-03-17 2006-09-21 Volodymyr Shpakovsky Method of producing corundum layer on metal parts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K. TZOGANAKOU ET AL: "Mobility of lithium ions in anodic alumina formed on an Al-Li alloy", CORROSION SCIENCE, vol. 42, no. 6, 1 June 2000 (2000-06-01), pages 1083 - 1091, XP055102031, ISSN: 0010-938X, DOI: 10.1016/S0010-938X(99)00130-4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876811A (zh) * 2020-07-27 2020-11-03 上海交通大学 一种铝锂合金微弧氧化方法及其采用的电解液
CN111876811B (zh) * 2020-07-27 2022-02-25 上海交通大学 一种铝锂合金微弧氧化方法及其采用的电解液

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EP2878712B1 (de) 2020-05-13

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