Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
  • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/021—Cleaning or etching treatments
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
  • C23C14/025—Metallic sublayers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/083—Oxides of refractory metals or yttrium
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/58—After-treatment
  • C23C14/5826—Treatment with charged particles
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/58—After-treatment
  • C23C14/5846—Reactive treatment
  • C23C14/5853—Oxidation
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
  • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
  • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
  • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
  • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
  • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
  • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
  • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Definitions

• the technical field relates to that of protective coatings deposited on a substrate, more specifically the protective coatings of a copper alloy substrate, that is to say formed at least on the surface of a copper alloy. in particular a brass or a bronze.
• the technical field also relates even more particularly to protective coatings for a substrate of the brass, bronze or equivalent type, said coating being obtained and/or deposited at least in part by vacuum physical vapor deposition of a thin film. protective.
• the field of the invention also relates to methods for producing and/or depositing such protective coatings on a substrate, in particular formed at least on the surface of a copper alloy, in particular a brass or a bronze.
• the field of the invention also relates to methods for producing and/or depositing such protective coatings comprising at least one step of physical vapor deposition under vacuum of a thin protective film.
• copper alloys have been developed, in particular those commonly called brass, comprising mostly a mixture of copper (chemical symbol Cu) and zinc (chemical symbol Zn), or alloys commonly called bronze, comprising mostly a mixture of copper (chemical symbol Cu) and tin (chemical symbol Sn).
• copper alloy is meant a cupro-alloy, that is to say an alloy comprising copper in which the copper content is predominant.
• a copper alloy has a lower melting temperature and better mechanical strength than pure copper, while retaining an implementation ease and improved corrosion resistance.
• the corrosion resistance of the alloy makes it possible to reduce corrosion but not to eliminate it, and it is necessary to provide a layer of protection against corrosion, in particular galvanic or atmospheric.
• brass-type copper alloys comprising mainly copper will be referred to by the general term “copper alloy” in the following description and claims. This includes bronzes and brasses in particular.
• Copper alloys are commonly used for the production of all types of objects, in particular small decorative and aesthetic objects.
• These copper alloy objects may have their surface covered in whole or in part by one or more layers.
• This may be one or more decorative layers, but also one or more mechanical protection layers, that is to say a layer having satisfactory resistance to mechanical wear and/or shock and/or scratching.
• mechanical protection layers that is to say a layer having satisfactory resistance to mechanical wear and/or shock and/or scratching.
• even one or more layers of protection of said material of the object against corrosion without of course counting a layer of primer or of adhesion to the material of the object.
• a layer presenting a resistance to mechanical wear and/or to shocks and/or to scratching satisfactory with regard to the expectations of the profession will be designated by the term "mechanical protection layer” in the following. of the description and the claims.
• PVD vacuum physical vapor deposition technology of a thin film
• ion deposition technology commonly called by the English term "ion”. plating”.
• This physical vapor deposition technology in English Physical Vapor Deposition, is more commonly known by its English acronym PVD. This so-called PVD technology is now widespread in industry.
• substrate refers to all or part of a brass object.
• thin layer is meant a layer less than 10 micrometers, or even sometimes less than 2 micrometers.
• This deposition by PVD is done in the presence of a so-called passive medium, that is to say under vacuum, or in the presence of a noble or so-called rare gas such as argon with the chemical formula Ar.
• This deposition can be also do so in the presence of a so-called active medium, that is to say in the presence of one or more so-called reactive gases, for example in the presence of dioxygen with the chemical formula O2, or dinitrogen with the chemical formula N2, or in the presence of a plasma, to obtain respectively for example an oxide or a nitride.
• PVD technology consists in using at least one metal or metal alloy target, installed with a substrate in an enclosure, in achieving a pressure reduction in the enclosure, and in transferring atoms from the target to the substrate, by passing them through a passive medium or an active medium.
• the substrate is mounted on a substrate holder, mobile or fixed in the enclosure.
• a target of a metal is composed of at least 99.5% of said metal.
• a metal alloy target is composed of at least 99.5% of a mixture of the metals constituting the corresponding alloy.
• target designates a target made of a metal or an alloy of several metals.
• the atoms or molecules can receive a quantity of energy in the form of waves until they reach, in the passive or active medium, a plasma state. Metal atoms then become metal particles. In the case of an active medium, metal atoms can also combine with reactive gases to form more complex particles.
• the particles Under the action of electric, magnetic or electromagnetic fields, the particles are accelerated in the direction of the substrate on which they are deposited and/or interact by forming covalent bonds. It is thus possible to form a thin layer of at least one metal derived from at least one target or from molecules on the substrate, or a thin layer of at least one metal combined with another metal, or a thin layer of at least one transition metal and at least one atom of a reactive gas on the substrate.
• transition metal or transition element is meant, according to the definition of the International Union of Pure and Applied Chemistry, "a chemical element whose atoms have an incomplete d electronic sub-shell, or which can form cations whose sub-shell electronic d is incomplete”.
• This transition metal can be in particular Chromium (with chemical symbol Cr), Titanium (with chemical symbol Ti), Zirconium (with chemical symbol Zr), Yttrium (with chemical symbol Y), Niobium, (with chemical symbol Nb), but it can also be Tungsten (chemical symbol W), Vanadium (chemical symbol V), Tantalum (chemical symbol Ta).
• a target made of an alloy of several metals it is also possible to use an alloy of several of the metals listed above.
• the primer layer thus formed on the substrate is thin, of the order of a few micrometers, and makes it possible to ensure good maintenance of the subsequent layers.
• the layer thus formed has, in known manner, a columnar microstructure, comprising inter-columnar spaces making this layer porous.
• This columnar microstructure allows the passage of a liquid, for example human sweat.
• This type of primer layer therefore does not make it possible to protect the substrate from corrosion due to the ambient atmosphere or from the touch of a person.
• transition metals have an oxidation-reduction potential also called electrochemical potential different from that of brass.
• An electrochemical couple or galvanic couple capable of causing a galvanic or electrolytic corrosion reaction in the presence of an electrolyte, such as human sweat, is then formed. This corrosion is done by the presence of two conductive metals in contact and in the presence of an electrolyte.
• the electrochemical potential difference between brass and titanium is of the order of 370 millivolts. It is also possible to measure an electrochemical potential difference between a cuprous alloy and a transition metal listed above.
• this type of primer layer formed by depositing a thin layer of a transition metal by PVD technology not only does not make it possible to protect the substrate from corrosion due to the ambient atmosphere. or a person's touch, but also accentuates the corrosion effect.
• a primer layer by electroplating, to then deposit on said primer layer a protective layer of a metal by electroplating, that is to say soaking in an electrolytic bath.
• the metal used may be nickel, chemical symbol Ni, but it is known to cause allergies during prolonged contact with the skin of some users.
• the metal used can also be a precious metal, such as palladium with the chemical symbol Pd, but the cost of such a coating then becomes high.
• the object of the invention is therefore to provide a coating for protecting a copper alloy substrate, in particular brass or bronze, on which it is applied corrosion, simple to implement and economical.
• Another object of the invention is to provide a protective coating for a copper alloy substrate applied to a copper alloy substrate, which can take on the characteristics of protection against corrosion, said coating comprising anti-corrosion characteristics. -corrosion, possibly resistance to mechanical wear and/or impact and/or scratching, as well as a decorative appearance similar to the characteristics of coatings of the prior art.
• Another object of the invention is to provide a method for producing such a protective coating, in particular anti-corrosion, on a copper alloy substrate.
• Yet another object is to provide a method for producing several protective and/or decorative layers on a copper alloy substrate.
• the invention relates to a protective coating of a copper alloy substrate, said protective coating comprising a primer layer, said primer layer being deposited on said copper alloy substrate, said layer primer being formed by a thin layer of at least one transition metal, said protective coating comprising a protective layer against corrosion, characterized in that said protective layer against corrosion is formed by at least a part of the primer layer, and in that said at least part of the primer layer is in the form of a combination of said at least one transition metal and said at least one oxidized transition metal.
• This protective coating is produced by PVD technology.
• the oxidation of the at least one transition metal takes place mainly on the surface of the primer layer opposite the substrate to form said protective layer against corrosion, in the form of a combination of said at least one transition metal and said at least one oxidized transition metal.
• the primer layer is also oxidized in depth, to a lesser extent.
• the primer layer deposited on said substrate has a percentage of at least one oxidized transition metal relative to at least one transition metal initially deposited, said percentage being minimal, including possibly zero, near the substrate, said percentage increases, at least on average, monotonically from said substrate in the direction of increasing distance from the substrate.
• This coating thus obtained has the advantage of having a protective layer against corrosion on the surface opposite that of the substrate, formed by a combination of said at least one transition metal and said at least one oxidized transition metal , this corrosion protection layer being a continuation of the primer layer in which the at least one transition metal is oxidized at gradually higher concentrations until reaching a maximum rate at said corrosion protection layer.
• the primer layer has, near the substrate, a percentage of at least one oxidized transition metal compared to at least one transition metal initially deposited, a minimum of 0%.
• the protective layer against corrosion has a maximum percentage of at least one oxidized transition metal relative to at least one initially deposited transition metal of between 95 and 100%.
• the primer layer comprising a part of at least one oxidized transition metal also comprises argon atoms inserted into the structure of the primer layer and the corrosion protection layer.
• the amount of argon atoms inserted into said structures is proportional to the percentage of at least one oxidized transition metal relative to at least one deposited transition metal initially present in said structures. This quantity is minimum close to the substrate, and increases as one moves away from the substrate to reach maximum values at the level of the protective layer against corrosion.
• argon is commonly used in PVD technology, as indicated above. Argon can block interstitial spaces of the initially columnar structure of at least one transition metal deposited by PVD. The modified structure no longer has as many interstitial spaces.
• argon being a chemically inert gas, it does not interact with corrosive chemical agents. The copper alloy is thus better protected against corrosion.
• This coating comprises a portion of at least one transition metal in oxidized form.
• the deposited structure, initially columnar of at least one transition metal, is modified and no longer has as many interstitial spaces.
• the copper alloy is thus better protected against corrosion.
• the protective coating comprises a mechanical protective layer, that is to say a layer having resistance to mechanical wear and/or to shocks and/or to scratching, this mechanical protective layer covering the corrosion protection layer.
• the mechanical protection layer comprises an adhesion layer and a functional layer.
• the tie layer is a thin layer of the same at least one transition metal as that used to form the primer layer.
• the functional layer is a thin layer of a nitride or an oxide or a carbide or an oxycarbide or a nitrocarbide of the same at least one transition metal as that used for form the primer layer.
• the protective coating comprises a decorative layer covering the mechanical protective layer.
• the decorative layer comprises at least one aesthetic layer.
• the aesthetic layer is a thin layer of a nitride or an oxide or a carbide or an oxycarbide or a nitrocarbide of the same at least one transition metal as that used to form the primer coat.
• the decorative layer also includes at least one tie layer for the aesthetic layer.
• the tie layer of the aesthetic layer is a thin layer of the same at least one transition metal as that used to form the aesthetic layer.
• said at least one transition metal is titanium.
• said at least one transition metal is chromium, or zirconium, or yttrium, or niobium, or tungsten, or vanadium, or tantalum.
• said primer layer of said protective coating is formed by a thin layer of an alloy of at least two transition metals from among titanium, chromium, zirconium, yttrium, niobium, tungsten, vanadium, and tantalum.
• the protective coating comprises a protective layer against corrosion with a thickness of between 0.2 and 1 micrometer, intervals included.
• the protective coating comprises a mechanical protective layer having an adhesion layer with a thickness of between 0.05 and 0.2 micrometers, intervals included, and a functional layer with a thickness of between 0.2 and 1 micrometer, intervals included.
• the protective coating comprises a decorative layer having an aesthetic layer with a thickness of between 0.2 and 1 micrometer, intervals included.
• the protective coating comprises a decorative layer also having an adhesion layer with a thickness of between 0.05 and 0.2 micrometers, intervals included.
• Such a protective coating deposited on a copper alloy substrate in particular a brass or a bronze, protects said copper alloy substrate from corrosion, it may comprise a mechanical protection layer on said corrosion protection layer, and a decorative layer on said protective layer on corrosion, or on the mechanical protective layer if such a layer covers said protective layer against corrosion.
• This coating makes it possible to protect copper alloy objects against corrosion on which it is deposited.
• these objects coated with this coating have excellent resistance to body sweat after a 24-hour test.
• no delamination of material was observed after salt spray tests for 96 hours and damp heat tests for 48 hours, according to the test methods of ISO 23160:2011, NF S80-772, NF EN ISO 4611, NF EN ISO 9227.
• This protective coating of a copper alloy substrate in particular a brass or a bronze, can have mechanical protection and decorative appearance characteristics similar to the characteristics of the coatings of the prior art.
• This protective coating of a copper alloy substrate deposited on said copper alloy substrate may include a mechanical protective layer also forming a decorative layer.
• the nickel release rate of this protective coating is, after verification, less than 0.04 pg/cm 2 week (microgram per square centimeter per week) with a maximum limit of 0.88 pg/cm 2 / week (microgram per square centimeter per week).
• the invention also relates to a method for depositing a protective coating of a copper alloy substrate on a copper alloy substrate by PVD technology, said method comprising the following steps: a) positioning said substrate on a substrate holder in an enclosure, b) a target consisting of at least one transition metal is installed in said enclosure and means for supplying different gases are connected to the enclosure, and a vacuum is produced, c) said copper alloy substrate is dehumidified and pickled, in particular by heating and/or ion etching, d) a thin layer of said at least one transition metal is deposited on said substrate by PVD technology until a primer layer is formed, e) the primer layer is bombarded of a mixture of argon ions and oxygen ions and forming a corrosion protection layer by oxidizing at least one transition metal of said primer layer so that said corrosion protection layer is formed by a portion of said primer layer, and said portion of said primer layer is in the form of a combination of said at least one transition metal and said at least one oxidized transition metal,
• the minimum percentage of at least one oxidized transition metal relative to at least one transition metal initially deposited is 0%.
• the maximum percentage of at least one oxidized transition metal relative to at least one transition metal initially deposited is between 95 and 100%.
• the primer layer once partially oxidized, has a gradient of oxides increasing away from the substrate up to the protective layer against corrosion formed, this protective layer against corrosion having a maximum quantity of oxides.
• step e) of the method described above in particular during the at least partial oxidation process of the primer layer, argon atoms are inserted into the primer layer. and the corrosion protection layer.
• the amount of argon atoms inserted during this process into said structures can be proportional to the percentage of at least one metal of oxidized transition with respect to at least one deposited transition metal initially present in said layers, and more particularly their layer structures. This quantity is minimum close to the substrate, and increases as one moves away from the substrate to present maximum values at the level of the protective layer against corrosion.
• a mechanical protection layer is deposited, that is to say that a grip layer of the at least one transition metal from the target and then depositing a thin layer of a nitride or a carbide or an oxide or an oxycarbide or a nitrocarbide formed from the combination of at least one transition metal from the target with respectively nitrogen, or carbon, or oxygen, or oxygen and carbon, or nitrogen and carbon from gases comprising nitrogen or carbon or oxygen injected into the enclosure by one or more gas supplies.
• a decorative layer is deposited, that is to say a thin layer is deposited. It can be a thin layer of a nitride or a carbide or an oxide or an oxycarbide or a nitrocarbide formed from the combination of at least one transition metal from the target with respectively l nitrogen, or carbon, or oxygen and carbon, or nitrogen and carbon from gases comprising nitrogen or carbon or oxygen injected into the enclosure by one or more power supplies in gas.
• a tie layer of at least one transition metal from the target can be deposited prior to the deposition of said layer described above in the paragraph.
• a protective coating is thus simply produced which protects the copper alloy substrate from corrosion and which may include a mechanical protective layer and/or a decorative layer.
• this method makes it possible to carry out all the steps for creating a protective coating using a single technology, PVD technology.
• the protective coating can also be produced simply with an addition of at least one transition metal from a single or several targets, which further facilitates handling and the manufacturing costs of this coating.
• FIG.1 is a schematic sectional view of a protective coating of a copper alloy substrate covering a copper alloy substrate, here a brass, said protective coating comprising a protective layer against corrosion , a mechanical protection layer, and a decorative layer, according to a particular embodiment of the invention.
• the invention relates to a protective coating 1 of a copper alloy substrate 2 deposited on a copper alloy substrate, here a brass.
• This substrate 2 can be a brass object, such as an ornament, a necklace or watch element.
• the protective coating 1 is considered here as deposited above the substrate 2 brass, and the top of said protective coating 1 deposited on said substrate 2 brass is located at the top of the figure 1 .
• Said substrate 2 to be covered can be brushed, sandblasted, polished, or have any other surface treatment that does not modify its surface composition.
• This protective coating 1 comprises a primer layer 3 deposited on said substrate 2 by deposition according to the PVD technology described above and known from the prior art.
• the PVD technology used may in particular be a physical vapor deposition technology by magnetron cathode sputtering, using a deposition chamber equipped with a target made of a transition metal, and gas lines allowing the supply of gas process such as argon gas and dihydrogen gas and reactive gases such as gases comprising nitrogen or oxygen, or carbon, such as dinitrogen gas, dioxygen gas or methane or acetylene gas.
• the primer layer 3 deposited on said substrate 2 has, according to a particular embodiment, a thickness of between 0.2 micrometer and 1 micrometer.
• the protective coating 1 includes a corrosion protection layer 4.
• this corrosion protection layer 4 is formed by part of the partially oxidized primer layer.
• This part of the partially oxidized primer layer forming the corrosion protection layer 4 comprises transition metal from primer layer 3 combined with transition metal from oxidized primer layer 3.
• This oxide formed modifies the structure of the initially primer layer 3 on part of said primer layer 3 and forms an anti-corrosion barrier protecting the substrate 2.
• the primer layer 3 deposited on said substrate 2 has a percentage of at least one oxidized transition metal relative to at least one initially deposited transition metal which increases as it moves away from the substrate 2.
• the primer layer 3 has near the substrate 2 a minimum percentage, for example 0%, this percentage increasing as the distance from said substrate 2 to reach a maximum percentage, between 95 and 100%, for example 99%, in the part of primer layer 3 forming the corrosion protection layer 4.
• the primer layer 3 comprising a portion of at least one oxidized transition metal may also comprise argon atoms inserted into the structure of the primer layer 3 and of the corrosion protection layer 4.
• the amount of argon atoms inserted into said structures may be proportional to the percentage of at least one oxidized transition metal relative to at least one deposited transition metal initially present in said structures. This quantity is then minimum near the substrate 2, and increases as one moves away from the substrate 2 to reach maximum values at the level of the protective layer 4 against corrosion.
• the corrosion protection layer 4 has, according to this particular embodiment, a thickness of between 0.2 micrometer and 1 micrometer, and constitutes part of the primer layer 3.
• the transition metal of the primer layer 3 and of the corrosion protection layer 4 is here titanium, but another transition metal can be used, such as for example chromium, zirconium, yttrium or niobium, tungsten, vanadium, tantalum, or any other transition metal capable of being oxidized at least partially to satisfactorily form a protective layer against corrosion.
• the primer layer 3 and the protective layer against corrosion 4 can be made not with a transition metal, but with an alloy of two or more transition metals among in particular titanium, chromium, zirconium, yttrium or niobium, tungsten, vanadium, tantalum, this alloy also being able to oxidize at least partially to form a satisfactory protective layer against corrosion.
• satisfactory protective layer we mean a protective layer making it possible to protect objects against corrosion according to 24-hour resistance tests, salt spray delamination tests for 96 hours and damp heat tests for 48 hours, according to the test methods of the ISO 23160:2011, NF S80-772, NF EN ISO 4611, NF EN ISO 9227 standards.
• the protective coating 1 can also comprise a mechanical protective layer 5 and a decorative layer 6.
• the mechanical protection layer 5 itself comprises a grip layer 50 covered by a functional layer 51 harder than the surface hardness of bare brass.
• the adhesion layer 50 is formed by depositing at least one transition metal using PVD technology on the protective layer against corrosion 4. This at least one transition metal may be identical to that or one of those used to form the primer layer 3. This at least one transition metal may be different if another target of at least one other transition metal is inserted into the enclosure and used to produce this layer .
• the functional layer 51 can be formed by depositing a nitride using PVD technology on the tie layer 50.
• This nitride is formed by a plasma, combining at least one transition metal which can be identical to that or one of those used to form the primer layer 3, and nitrogen from a gas comprising nitrogen.
• This at least one transition metal may be different if another target of at least one other transition metal is inserted into the enclosure and used to produce this layer.
• the functional layer 51 can alternatively be formed by depositing a carbide, an oxide, an oxycarbide or a nitrocarbide using PVD technology instead of the nitride deposit formed by combining at least one transition metal which may be identical to that or one of those used to form the primer layer 3 and respectively carbon, or oxygen, or oxygen and carbon, or nitrogen and carbon from gases comprising nitrogen or carbon or oxygen injected into the enclosure.
• the decorative layer 6 here itself comprises a grip layer 60 covered by an aesthetic layer 61.
• the adhesion layer 60 is formed by depositing a transition metal using PVD technology on the protective layer against corrosion 4, or on the functional layer 51 in the case of a prior deposit of a mechanical protection layer 5 on the corrosion protection layer 4.
• This transition metal can be identical to that used to form the primer layer 3.
• This transition metal can be different if another target from another transition metal is inserted into the enclosure and used to make this layer.
• the decorative layer 6 may not include a grip layer 60.
• the decorative layer 6 then only includes an aesthetic layer 61.
• the aesthetic layer 61 can be formed by depositing a nitride using PVD technology on the adhesion layer 60 of the decorative layer 6, or on the mechanical protection layer 5 if the decorative layer 6 does not does not have a tie layer 60.
• This nitride is formed by a plasma combining at least one transition metal which may be identical to that or one of those used to form the primer layer 3 and nitrogen from a gas comprising nitrogen. This at least one transition metal may be different if another target of at least one other transition metal is inserted into the enclosure and used to produce this layer.
• the aesthetic layer 61 can alternatively be formed by depositing a carbide, an oxide, an oxycarbide or a nitrocarbide using PVD technology instead of the nitride deposit, formed by combining at least one transition metal which may be identical to that or one of those used to form the primer layer 3 and respectively carbon, or oxygen, or oxygen and carbon, or nitrogen and carbon from gases comprising nitrogen or carbon or oxygen injected into the enclosure.
• the mechanical protective layer 5 can also be a decorative layer 6, according to an embodiment of the invention not illustrated here.
• the functional layer 51 is then also an aesthetic layer 61.
• the protective coating 1 deposited on the substrate 2 comprises a mechanical protective layer 5 having an adhesion layer 50 with a thickness of between 0.05 and 0.2 micrometer, intervals included , and a functional layer 51 with a thickness of between 0.2 and 1 micrometer, intervals included.
• the protective coating 1 deposited on the substrate 2 can also comprise a decorative layer 6 having an adhesion layer 60 with a thickness of between 0.05 and 0.2 micrometers, intervals included, and a layer of aesthetics 61 with a thickness of between 0.2 and 1 micrometer, intervals included.
• the decorative layer 6 covers the mechanical protection layer 5.
• the substrate 2 covered with a protective coating 1 according to the invention was subjected to wear tests carried out with Turbula®, to adhesion tests, including the grid test, and to climatic tests involving artificial sweat, salt spray, damp heat and moist heat in the presence of leather.
• the invention also relates to a process for depositing a protective coating of a copper alloy substrate on a copper alloy substrate, in particular a brass or a bronze, by PVD technology.
• a protective coating of a copper alloy substrate on a copper alloy substrate in particular a brass or a bronze
• PVD technology An example of a method is described below.
• This method comprises the following steps: a) said substrate 2 is positioned on a substrate holder in an enclosure used to carry out a deposition by PVD technology.
• This substrate 2 may have been washed and/or degreased with different detergents, rinsed and dried before being positioned in the substrate holder.
• This substrate 2 is here a brass composed of 58% copper and 42% zinc by mass.
• a target made of at least one transition metal is installed in the enclosure.
• the at least one transition metal is, in the example described below, titanium Ti.
• Means for supplying various gases, in particular argon gas, dioxygen gas, dihydrogen gas and dinitrogen gas, are also connected to the enclosure.
• the gas supply means are for example gas supply networks connected to gas cylinders.
• Vacuum pumps are also put into action to create a vacuum in the enclosure down to a starting pressure between 5 ⁇ 10 5 and 1 ⁇ 10 7 millibars, intervals included.
• the brass substrate 2 is prepared, that is to say that said substrate 2 is dehumidified by heating, and said substrate 2 is pickled in order in particular to remove the oxides which may be present on said substrate 2; this pickling being done by ionic pickling.
• the heating is done between 200 to 300° Celsius, intervals included, to remove possible moisture residues and improve adhesion to the substrate 2.
• the ion stripping can be carried out by passing over the substrate 2 a plasma obtained from an argon/hydrogen mixture, with a argon/hydrogen ratio by volume between a 98/2 ratio and an 80/20 ratio, intervals included, and this to prepare the surface state of the substrate 2.
• a thin layer of titanium is deposited by PVD technology on the substrate 2 until a primer layer 3 is formed. To do this, titanium is transferred from the target to the substrate 2. This deposition is done here by sputtering for a time between 10 to 30 minutes, time intervals included, under sweeping of an argon gas flow with a flow rate of between 200 to 300 cm3/minute, intervals included, at an argon gas density defined by standard temperature and pressure conditions, i.e.
• the primer layer 3 thus formed has a thickness of between 0.2 micrometer and 1 micrometer, intervals included. e) once the primer layer 3 has been formed on the said substrate 2, the top of the said primer layer 3 is bombarded for a time comprised between 3 and 10 minutes, intervals included, with a plasma of argon ions and d oxygen ions.
• a protective layer 4 against corrosion is thus formed by modifying at least part of the primer layer 3.
• This at least part of the primer layer 3 comprises titanium combined with oxidized titanium.
• This at least part of the primer layer 3 may also comprise other compounds formed by other combinations of titanium atoms alone, oxygen atoms alone or titanium atoms combined with titanium atoms. 'oxygen. f) according to an additional and optional step, a mechanical protection layer 5 is produced on the corrosion protection layer 4.
• a thin layer of titanium is deposited to form a layer hook 50 with a thickness of between 0.05 and 0.2 micrometers, intervals included.
• a layer of titanium nitride resulting from the combination of titanium atoms resulting from the target with nitrogen atoms resulting from a dinitrogen gas in the chamber is deposited.
• a mechanical protection layer 5 is thus formed which has a thickness of between 0.2 and 1 micrometer, intervals included g) according to another additional and optional step, a decorative layer 6 is produced on the protection layer 4 against corrosion , or on the mechanical protection layer 5 in the case where the method carries out step f).
• a thin layer of titanium is deposited to form a bonding layer 60 with a thickness of between 0.05 and 0.2 micrometers, intervals included.
• a layer of titanium nitride resulting from the combination of titanium atoms resulting from the target with nitrogen atoms resulting from a gas comprising nitrogen, such as for example nitrogen gas in the enclosure is thus formed which has a thickness of between 0.2 and 1 micrometer, intervals included.
• the oxidation is varied so that said primer layer 3 has a percentage of at least one transition metal oxidized relative to at least one transition metal initially deposited which increases away from the substrate 2, exhibiting an oxidation gradient.
• the primer layer 3 has a minimum percentage near the substrate 2, for example 0 to 1%, this percentage increasing as the distance from said substrate 2 increases. to reach a maximum percentage between 95 and 100%, for example 99%, in the part of primer layer 3 which forms the corrosion protection layer 4.
• argon atoms are inserted into the primer layer 3 and the layer of corrosion protection 4.
• the quantity of argon atoms inserted during this process into said layers is proportional to the percentage of the at least one transition metal oxidized with respect to at least one transition metal deposited initially present in said layers. This quantity is minimum near the substrate 2, and increases as one moves away from the substrate 2 to present maximum values at the level of the protective layer against corrosion 4.
• the mechanical protection layer 5 formed by step f) is also a decorative layer 6.
• the total thickness of the protective coating 1 is thus reduced.
• a layer of titanium nitride is used to obtain a decorative layer of yellow color.
• a decorative layer of white color it is possible to deposit a layer of chromium nitride. It is then necessary to provide, in step b) of the method described above, to also insert a chromium target into the enclosure in addition to the titanium target to form a chromium grip layer 60 and then a aesthetic layer 61 of chromium nitride according to step g).
• This decorative chrome layer can cover the mechanical protective layer of titanium and titanium nitride, as illustrated in FIG.
• the decorative layer 6 can of course have other colors depending on the metal or metal alloy used and deposited to form said decorative layer 6.
• transition metals other than titanium it is also possible to use one or more transition metals other than titanium to form a protective coating 1 deposited on a substrate 2 made of copper alloy, in particular a brass.
• transition metal other than titanium it is also possible to use a transition metal other than titanium to form all or part of the protective layer 4 against corrosion, of the mechanical protective layer 5 or the decorative layer 6 of a protective coating 1 deposited on a substrate 2 of copper alloy, in particular a brass.
• the various stages of the process for manufacturing the coating with or without mechanical protective layer 5 and/or decorative layer 6 are carried out in a single vacuum charge and without venting the substrate 2.
• this method can be applied to several substrates at the same time, in particular mounted on a substrate holder having moving parts in the enclosure, and can use several identical or different targets.
• the method described above makes it possible to produce a protective coating 1 deposited on a substrate 2 of copper alloy, having all or part of the characteristics of the protective coating 1 deposited on a substrate 2 of copper alloy according to the invention described. above.
• a protective coating 1 deposited on a copper alloy substrate 2 according to the invention described above can be produced by implementing the method described above, including or not step f) and/or step g).
• This process for depositing a protective coating on a copper alloy substrate is particularly suitable for a brass or bronze substrate.
• This protective coating is particularly suitable for protecting a brass or bronze substrate from corrosion.

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• 2022
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