EP3294926B1 - Procédé de traitement de surface d'un alliage de magnésium et procédé de dépôt autocatalytique de nickel sur une surface traitée - Google Patents

Procédé de traitement de surface d'un alliage de magnésium et procédé de dépôt autocatalytique de nickel sur une surface traitée Download PDF

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EP3294926B1
EP3294926B1 EP15709985.4A EP15709985A EP3294926B1 EP 3294926 B1 EP3294926 B1 EP 3294926B1 EP 15709985 A EP15709985 A EP 15709985A EP 3294926 B1 EP3294926 B1 EP 3294926B1
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Prior art keywords
component
process according
bath
magnesium
magnesium alloy
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German (de)
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EP3294926A1 (fr
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Emanuele Albanese
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Dbs Group International Trust Co Srl
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Dbs Group International Trust Co Srl
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    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline compositions for etching other metallic material
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1669—Agitation, e.g. air introduction
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1676—Heating of the solution
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals

Definitions

  • Magnesium is an alkaline hard metal with a density 1,76 g/cm3, of white silver colour and is one of the more widespread element on the planet.
  • Magnesium has a low thermal specific capacity and latent heat relatively low. Further, magnesium has a low affinity with the steel and is easily to recycle.
  • Magnesium has an excellent castability, high dimensional stability, high ratio resistance-specific weight, a low melting point, good electromagnetic shielding and very good mechanical properties.
  • magnesium oxide that, when is in form of dust, may develop an exothermic reaction in the presence of oxygen and water vapour.
  • the magnesium is less noble than other materials (lower potential electronegative) and tends to corrode easily.
  • nickel plating or electroless nickel plating chromium plating, galvanizing, oxidizing, silver plating, gold plating, palladium plating.
  • the base material needs a specific preliminary superficial pre-treatment and the type of pre-treatment is specific for each kind of base material.
  • a common problem of metallization processes is the cleaning of the surface of the base material. This cleaning allows the coating material to best adhere to the base material.
  • Coating layers may also be manifold to sum effects of each layer.
  • ABS or aluminium are coated with copper, nickel and chrome.
  • the hard anodizing allows only a black or white superficial coloration and thus is applied where no particular aesthetic finishing are required.
  • the process known with the commercial name keronite is a process of superficial conversion of light alloys as aluminium, titanium and magnesium alloys, where, through a source of high energy within a gas, the natural oxide of the base material is expanded till a very compact and thick structure is realized, similar to ceramic carryovers.
  • This compact structure makes the material very wear proof and gives a good corrosion protection degree.
  • the keronite is not applicable to all the typologies of products made of magnesium alloy.
  • the high current density may bring defects in the objects with complex geometries and in particular in the undercuts and in some critical points where the deposit cannot arrive.
  • method known from the state of the art does not improve adhesion of the metallization to the surface of a component made of magnesium alloy, in particular the metallization is a process of nickel plating.
  • method known from the state of the art does not provide a method that allows to avoid use of carcinogen products, as chromic acid and its hexavalent salts, used in the traditional processes of metallization and passivation.
  • a further problem known from the state of the art is connected to the corrosion that often occurs during nickel plating process. During this process magnesium may corrode to protect nickel deposit.
  • the object of the present invention is to overcome drawbacks of the state of the art.
  • the process to treat the surface of magnesium alloy is a first object of the present invention.
  • the electroless nickel plating adheres promptly to the surface made of magnesium alloy.
  • Said superficial treatment prepares in an economic and effective way, the surface of the magnesium alloy object to receive a subsequent process of electroless nickel plating that represents the second object of the present invention.
  • the magnesium alloy object is uniformly covered of a coating of nickel plate that allows to coat the object with further superficial finishings.
  • the deposit of nickel plate on the surface of the magnesium alloy object makes the surface electrically conductive, for applications requiring such feature.
  • the processes of the first and second objects of the present invention are not carried out in an acid environment, making them much safer than the ones known from the state of the art.
  • the electroless nickel plating not carried out in an acid environment, allow avoiding the corrosive phenomenon of the magnesium alloy that often occurs during electroless nickel plating of the alloy itself.
  • the nickel coating has an excellent adhesion degree to the substrate of magnesium alloy.
  • Fig. 1 shows a block diagram according the present invention, that schematically shows the step of the superficial treatment method of a magnesium alloy and the electroless nickel plating of the pre-treated surface.
  • figure 1 To properly comprising the idea underlying the present invention, reference to figure 1 is made.
  • the superficial treatment process 100 of an object made of magnesium alloy comprises various steps described in detail below.
  • step 110 an object or component realized at least in its surface with a magnesium alloy is provided.
  • the component may optionally rinsed with water after the moulding.
  • the impurities on the surface for example oil
  • the impurities on the surface of the component may be as well present magnesium hydroxide spontaneously formed on the magnesium alloy for protective reasons.
  • the component to pre treat has a low superficial finishing, e.g. because has scraps or chips deriving from the manufacturing process, it is possible superficially finishing the component with a mechanical machining with the aid of an alkaline substance, for example the substance known with the trade name Quakercool 3890 of the company Quaker.
  • an alkaline substance for example the substance known with the trade name Quakercool 3890 of the company Quaker.
  • a tape or brush polishing or a vibro-finishing with dedicated machines can be used as mechanical machining.
  • the surface of the component is chemically degreased (step 120) through an agitated water solution, preferably with insufflated air, and containing salts of borax, like borax decahydrate, tetra borate sodium, decahydrate or borate sodium in a weight percentage comprised between 25% and 50 %, pyrophosphate salts, as pyrophosphate sodium, in a weight percentage comprised between 2,5% and 10 %, sulfonated sodium salts, as dodecylbenzene sulfonated sodium, in a weight percentage comprised between 2,5% and 10 %, and a surfactant, e.g. ethoxylate alcol, in a weight percentage comprised between 2,5% and 5 %.
  • borax like borax decahydrate, tetra borate sodium, decahydrate or borate sodium
  • pyrophosphate salts as pyrophosphate sodium
  • sulfonated sodium salts as dodecylbenzene sulfon
  • the time span of the step 120 of chemical degreasing, the immersion time of the component in the bath, depends from the type of alloy.
  • the time span of this step 120 is inversely proportional to the presence of aluminium in the alloy.
  • the time of immersion for alloys like AZ91, AZ31 and AZ21 is between 5 and 10 minutes, whilst for alloys AM 50, AM 60, ZK30 and ZK60 the time of immersion is between 10 and 30 minutes.
  • the time span of the step 120 depends, for the same alloy, and the type of casting used.
  • a time of immersion between 10 and 15 minutes, whilst if the component is made by injection the time of immersion is preferably of 5 - 8 minutes, because the surface is less porous and more compact.
  • the time of immersion is preferably of 20 - 30 minutes, because the surface is more porous and manufacturing residues may be present. This step 120 may thus last from 5 to 30 minutes according the manufacturing process by which the component is realized.
  • the surface of the component made of a magnesium alloy may be rinsed to remove degreasing substances of the previous chemical degreasing step (step 120).
  • This step occurs to avoid degreasing substances of the previous steps are present in the phases subsequent the rinsing.
  • the rinsing phase may be ended when the operator looking on the surface of the component sees a uniform film of water on it.
  • the present rinsing phase ends in 15 minutes.
  • step 130 other than magnesium hydroxide, that is spontaneously formed on the magnesium alloy, are removed superficial imperfections, for examples chippings or scraps of the metal, that could in turn oxidized from the production process.
  • said bath is at ambient temperature and is in a tank realized in steel 316L, internally coated in plastisole or Moplen (Polypropylene-H) to avoid degreasing agents act also on the steel instead of the component. Furthermore the ammonium bifluoride is corrosive for the steel.
  • the tank is mechanically agitated or through air to mix the solution and thus makes the reaction more effective.
  • Times of immersion of the component in the bath depend on the type of alloy as a function of the oxide in the component. Different alloys have different affinities to develop magnesium hydroxide on their surface. The more magnesium hydroxide is present on the surface of the component and the longer is the length of the step.
  • alloy AZ91 an immersion time of 2 - 5 minutes is preferable
  • alloys AZ31, AZ21, ZK30 and ZK60 an immersion time of 20 - 60 seconds is preferable, whilst for alloys AM50 and AM60 an immersion time of 1 - 3 minutes is preferable.
  • time span of the superficial oxide removal step (step 130) depends, for the same alloy, from the type of casting used. Manufacturing techniques influences production on the formation of oxide on the surface. If the component is made by extrusion or lamination time of immersion is of 2 - 3 minutes is preferable, by injection a time of immersion of 30 - 90 seconds is preferable, while components made by casting and/or moulding a time of immersion between 1 and 5 minutes is preferable.
  • the surface of the component made of magnesium alloy may be rinsed in demineralized water at ambient temperature.
  • the water is demineralized to avoid the salts contained influence the reactions of the following steps.
  • the tank containing the rinsing water be agitated by air insufflation to augment the efficacy of the step.
  • the rinsing step ends in 5 minutes.
  • the component After the preceding step of rinsing of the surface, the component has for a first time a superficial activation (step 140) to enucleate on the component surface magnesium fluoride (MgF 2 ).
  • this step 140 generates magnesium fluoride (MgF 2 ) between the ⁇ primary, ⁇ eutectic and ⁇ phases of the crystalline structure of the magnesium alloy.
  • step 140 a plurality of catalyzable zones are realized on the surface of the material to coat and the oxidation-reduction reaction of the chemical nickel may start.
  • step 140 the component is immerse in a bath containing fluoride salts with a concentration of 280-345 g/l and phosphoric acid (H 3 PO 4 ) with a concentration of 20-70 ml/l.
  • fluoride salts may be hydrofluoric acid (HF) or ammonium bifluoride ((NH 4 )HF 2 ), for the behaviour of the magnesium to bond with the fluoride to form magnesium fluoride (MgF 2 ).
  • Phosphoric or sulphuric acid augments the solubility of the fluoride salts in the bath.
  • the bath is at a temperature comprised between 35°C and 50°C, preferably 40°C, and occurs in a tank, preferably realized in steel 316L, internally coated in plastisole or Moplen (Polypropylene-H) to avoid degreasing agents of the bath act also on the steel of the tank instead of the component. Furthermore the ammonium bifluoride is corrosive for the steel.
  • the tank is mechanically agitated and comprises a filter pump with a porous septum, preferably of
  • immersion times depend of the manufacturing technique used. For moulding or cast, is preferable an immersion time of 2-5 minutes. For injections, is preferable an immersion time of 30-90 seconds. For extrusion and lamination, is preferable an immersion time of 2-3 minutes.
  • the time span of the present step 140 is proportional to the superficial porosity degree.
  • the tank containing rinsing water be agitated by air insufflation or alternatively by ultrasounds, to augment the efficacy of this step.
  • the present rinsing step lasts preferably less than 90 seconds, to avoid the surface of the component, that is extremely active from the previous phase, reacts with hydrogen and oxygen to form again magnesium hydroxide (Mg(OH) 2 ).
  • This rinsing step allow to eliminate traces of the previous steps that could react with the pyrophosphate salt of the next step.
  • the tank is agitated, preferably mechanically agitated, and comprises a filter pump.
  • the filter of the pump has a porous septum of 5-10 ⁇ m, to avoid that solids detached from the component is again in contact with the surface of the component immersed in the bath.
  • the filter pump continually cleans the solution in the tank.
  • the tank is preferably realized in steel 316L and internally coated in plastisole or Moplen (Polypropylene-H) to avoid degreasing agents react with the steel instead of the component, and to avoid that nitrates damage the steel of the tank.
  • plastisole or Moplen Polypropylene-H
  • immerging times depend from the manufacturing process.
  • a time of immersion between 2 and 4 minutes, whilst if the component is made by injection the time of immersion is preferably of 1-3 minutes, if the component is made by extrusion or lamination the time of immersion is preferably of 3 - 8 minutes.
  • the time span of this step 150 is directly proportional to superficial porosity degree. This step may vary from 20 seconds to 8 minutes according to manufacturing process used for realizing the component and to the type of magnesium alloy of the component.
  • step 150 there is the rinsing of the component surface in demineralized water at ambient temperature.
  • the water is demineralized to avoid the salts contained influence the reactions of the following steps.
  • the tank containing rinsing water be agitated by air insufflation or alternatively by ultrasounds, to augment the efficacy of this step.
  • the present rinsing step lasts preferably less than 90 seconds, to avoid that the surface of the component, that is extremely active from the previous phase, reacts with hydrogen and oxygen to form again magnesium hydroxide (Mg(OH) 2 ). This further rinsing step allows eliminating traces of the previous steps that should pollute the subsequent one.
  • the component is realized through injection the following steps are not necessary, therefore it is possible to extend the time span of the second activation until 10 minutes.
  • the components realized by injection have a poor porosity and that allows to obtain a quick degree of levelling of the surface and a compact and uniform growth of magnesium fluoride.
  • the component made of magnesium alloy may be rinsed in demineralized water at ambient temperature.
  • the water is demineralized to avoid the salts contained influence the reactions of the following steps.
  • the component is realized with a manufacturing process, or moulding process, giving a surface particularly porous and irregular it is preferable keep going the superficial treatment of the component with the following steps. It is therefore preferable keep going the process for components manufactured with techniques different to injection.
  • the surface of the component is newly uniformed by etching, to level the residual imperfections of the component surface.
  • the surface of the component is uniformed where the crystalline structure is more discontinue.
  • the porosity if any are in practice levelled.
  • the bath contains, dissolved in water, pyrophosphate salts, as tetrapyrophosphate potassium (K 4 P 2 O 7 ), in a concentration of 30-50 g/l, and nitrate salts, as potassium nitrate (KNO 3 ), in a concentration of 30-50 g/l.
  • pyrophosphate salts as tetrapyrophosphate potassium (K 4 P 2 O 7 )
  • nitrate salts as potassium nitrate (KNO 3 )
  • the tank is agitated, preferably mechanically agitated, and comprises a filter pump.
  • the filter pump has a porous septum, preferably of 5-10 ⁇ m, to avoid that solids detached from the component (if any) is again in contact with the surface of the component immersed in the bath.
  • the filter pump continually cleans the solution in the tank.
  • the tank is preferably realized in steel 316L and internally coated in plastisole or Moplen (Polypropylene-H) to avoid the substances of the bath react also on the steel instead of the component. This to avoid that the nitrates damage the steel of the tank.
  • the time span of this step depends from the porosity degree of the surface at the beginning of the step. Determinant factors for time span of the etching step are typology of the manufacturing process and the type of alloy.
  • magnesium alloys are more sensible to pyrophosphate salts e.g. alloy without aluminium as ZK30 alloy and the time span of the etching is brief, while for alloys with more aluminium, as AZ91, the time span of the etching lasts more.
  • alloys AZ91 and AZ21 are preferable immerging the component in the bath for 2-4 minutes
  • alloy AZ31 is preferable immerging the component in the bath for 40 - 90 seconds
  • alloys ZK30, ZK60, AM50 and AM60 is preferable immerging the component in the bath for 20 - 60 seconds.
  • immerging times depend from the manufacturing process.
  • the duration of this step may vary from 20 seconds to 8 minutes according on function of the manufacturing process and of the type of magnesium alloy of the component.
  • the component made of magnesium alloy may be rinsed in demineralized water at ambient temperature.
  • the water is demineralized to avoid the salts contained influence the reactions of the following steps.
  • the tank containing the rinsing water be agitated by air insufflation to augment the efficacy of the step.
  • the rinsing step ends preferably in less than 60 seconds, to avoid that surface of the component, that is extremely active from the previous phase reacts with hydrogen and oxygen to form again magnesium hydroxide (Mg(OH) 2 ).
  • the component After the preceding step of rinsing of the surface, the component has for the third time a superficial activation to enucleate on the surface further magnesium fluoride (MgF2). Following the previous removal of the magnesium hydroxide from the surface (step 130), this step 140 generates magnesium fluoride (MgF2) between the ⁇ primary, ⁇ eutectic and ⁇ phases of the crystalline structure of the magnesium alloy.
  • MgF2 magnesium fluoride
  • This step of the process has the double scope of protecting the surface, since the magnesium fluoride (MgF 2 ) is substituted by magnesium hydroxide (Mg(OH) 2 ) that normally would form on the surface, and making the surface catalyzable at electroless nickel plating.
  • MgF 2 magnesium fluoride
  • Mg(OH) 2 magnesium hydroxide
  • the component is immersed in a bath containing fluoride salts with a concentration of 280-345 g/l and phosphoric acid (H 3 PO 4 ) with a concentration of 20-70 ml/l.
  • fluoride salts may be hydrofluoric acid (HF) or ammonium bifluoride ((NH 4 )HF 2 ), for the behaviour of the magnesium to bond with the fluoride to form magnesium fluoride (MgF 2 ).
  • Phosphoric or sulphuric acid augments the solubility of the fluoride salts in the bath.
  • the bath is at temperature comprised between 35°C and 50°C, preferably 40°C, and occurs in a tank preferably realized in steel 316L, internally coated in plastisole or Moplen (Polypropylene-H) to avoid degreasing agents act also on the steel of the tank instead of the component. Furthermore the ammonium bifluoride is corrosive for the steel.
  • the tank is mechanically agitated and comprises a filter pump with a porous septum, preferably of 5-10 ⁇ m, to avoid that solids detached from the component is again in contact with the surface of the component immersed in the bath.
  • the filter pump continually cleans the solution in the tank. It is not advisable the use of tanks agitate by air insufflation, since the oxygen may modify the activation reaction.
  • immersion times depend of the manufacturing technique used. For moulding or cast, is preferable an immersion time of 7-12 minutes. For extrusion and lamination, is preferable an immersion time of 2-4 minutes.
  • the time span of this step may thus last from 2 minutes to 12 minutes according to the manufacturing process used and the magnesium alloy in which the component is made.
  • the component made of magnesium alloy may be rinsed in demineralized water at ambient temperature. It is further preferable the tank containing the rinsing water be agitated by air insufflation to augment the efficacy of the step.
  • the rinsing step ends in less than 60 seconds, to avoid the the surface of the component, that is extremely active from the previous phase, reacts with hydrogen and oxygen to form again magnesium hydroxide (Mg(OH) 2 ).
  • the surface of the component is ready for the electroless nickel plating.
  • the surface has only few traces of magnesium hydroxide but vice versa many areas where magnesium fluoride (MgF 2 ) is present.
  • the pre-treated component is then immersed in an alkaline bath containing nickel with a low quantity of phosphor (step 170), namely from 1 to 3 in weight percentage.
  • the bath may have a temperature comprised between 74°C and 85°C and containing nickel sulphate (NiSO4), sodium hypophosphite (NaPO 2 H 2 ) and regulators of the chemical oxidation-reduction reaction.
  • NiSO4 nickel sulphate
  • NaPO 2 H 2 sodium hypophosphite
  • the concentration of nickel sulphate (NiSO4) is preferably comprised between 5 g/l and 6,5 g/l and that of sodium hypophosphite (NaPO 2 H 2 ) is preferably comprised between 15 g/l and 25 g/l.
  • the sodium hypophosphite (NaPO 2 H 2 ) is the regulating element of the concentration of phosphor in the alloy and augmenting it augments the concentration of phosphor in the alloy.
  • the nickel sulphate reacts by oxidation-reduction with sodium hypophosphite and metal nickel falls on the surface of the component.
  • Compounds fluoride are promoter of the oxidation-reduction reaction between nickel sulphate and sodium hypophosphite, the magnesium alloy becomes catalytic and begins to cover with nickel metal. Consequently, the nickel metal deposits on the surface of the component. In this process sodium hypophosphite becomes orthophosphite sodium.
  • regulators of the chemical reaction of oxidation-reduction may comprise: carbocyclic acids with a complex concentration between 20 and 90 g/l, e.g. succinic acid (C 4 H 6 O 4 ), malic acid (C 4 H 6 O 5 ), lactic acid (CH 3 H 6 O 3 ) e citric acid (CH 6 H 8 O 7 ); ammonium fluoride (NH 4 F) with a content between 7,2 and 12,3 g/l; ammonium sulphate ((NH 4 ) 2 SO 4 ) with a content between 1,2 and 2,8 mg/l; and trisodium citrate (Na 3 C 6 H 5 O 7 ) with a content between 3,8 and 11,7 g/l.
  • carbocyclic acids with a complex concentration between 20 and 90 g/l
  • succinic acid C 4 H 6 O 4
  • malic acid C 4 H 6 O 5
  • lactic acid CH 3 H 6 O 3
  • e citric acid CH 6 H 8 O 7
  • ammonium fluoride and ammonium sulphate are accelerator of the reaction, whilst the carbocyclic acids and trisodium citrate are complexants and stabilizers of the reaction.
  • the bath is contained in a tank comprising:
  • the aforementioned means for maintaining the content of nickel sulphate and sodium hypophosphite may comprise two containers containing the solution of nickel sulphate and sodium hypophosphite connected with the tank where the component is immersed and a controller configured to regulate the dispensing of the two compounds in the bath to maintain steady contents.
  • Means for maintaining an alkaline pH in the bath may comprise a pHmeter to control if the pH lowers than 6 and a pump taking sodium hydroxide, preferably with a content equals to or inferior to the 10%, from another container.
  • Sodium hydroxide is not directly inserter in the tank with the electroless nickel plating, otherwise the nickel hydroxide flocculates forming by reaction between the sodium hydroxide and nickel phosphate. It is thus preferable dosing the sodium hydroxide inside the pump installed.
  • Means for agitating the bath may be mechanical, as mobile frame moved in the bath, wherein the components to treat are attached.
  • the tank may comprise a filter pump to delicately agitate the bath without air insufflation. It is preferable a filtration with 6-7 exchanges per hour.
  • the pump has preferably a capacity of 600-700 l/h.
  • the tank may be in stainless steel 316L with anodic protection, preferably at 650 mVolt, and steam heating. It is preferable to avoid heating system with candles in pirex glass, these would be damaged from substances in the nickel solution, e.g. from fluorides.
  • the deposit generated on the surface of the component has a thickness and an aspect substantially uniform and furthermore a low content of phosphor.
  • the deposit of the nickel so obtained is sufficiently hard, few passive and adapted to receive further layers of coating.
  • the component so nickel plated is particularly resistant to the corrosion and the abrasion, because the layer of nickel obtained on the component makes a uniform barrier between air and the surface of the material made of magnesium alloy.
  • Alloy AZ91D is the magnesium alloy more widespread and comprises about 9% aluminium and 1% zinc.
  • the process comprises a rinsing phase with demineralized water in an agitated tank.
  • the nickel plated component according the process of the present invention may subsequently have further superficial treatments, with functional or aesthetic features, according one of the following processes.
  • the first process of further superficial treatment comprises a neutralization step, an alkaline copper plating a further electroless nickel plating with a content medium/high of phosphor a passivation step to increment the resistance to corrosion and a drying step and a thermic treatment.
  • An nickel plate alloy with a medium content of phosphor comprises a weight percentage of phosphor comprised between 4 and 9, whilst an alloy with a high content of phosphor comprises a weight percentage of phosphor comprised between 10 and 12.
  • This first process allows improving resistance to corrosion and wear of the component.
  • a second process of further superficial treatment comprises a neutralization step, a step of alkaline copper plating, a further electroless nickel plating with a content medium/high of phosphor, a superficial activation step, a step of lamellar zinc and a final superficial coating with painting.
  • This second process allows further improving resistance to corrosion and represents an alternative to the classical painting.
  • a third process of further superficial treatment comprises an activation step of superficial activation and a DLC step (Diamond Like Carbon).
  • This third process allows improving resistance to wear of the component reaching superficial hardness up to 5200 HV.
  • a fourth process of further superficial treatment comprises a neutralization step and a step of alkaline zinc plating.
  • a fifth process of further superficial treatment comprises a step of neutralization, a step of alkaline copper plating, a step of neutralization a further step of acid copper plating, a step of neutralization, a step of electroless nickel polished plating, a step of electrolytic nickel opaque, a step of neutralization, a step of activation, a step of micro porous chrome plating, and in the end a step of polished chrome plating, satin finish chrome plating, opaque or black.
  • the polished nickel plating provides polished finishing to the next chrome plating, whilst the opaque nickel, as known as nickel columnar, provide a higher corrosion resistance.
  • This seventh process allows component to be used for every common application, for example for bath fitting components or door knobs.
  • a eight process of further superficial treatment comprises a neutralization step, an alkaline copper plating, a further step of neutralization, a further step of alkaline copper plating, a step of neutralization, an acid copper plating, a step of neutralization, a step of tin-copper alloy plating, a new step of neutralisation, a golden, palladium or silver plating step, a step of gun metal or white bronze.
  • Gun metal is a deposit dark and polished, while white bronze is a silver looking deposit.
  • This ninth process allow the component having a particularly pleasant aesthetic superficial finishing.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • ing And Chemical Polishing (AREA)

Claims (15)

  1. Procédé de traitement de la surface d'un alliage de magnésium comprenant les étapes de:
    I - fournir un composant en alliage de magnésium et fabriqué par un processus de production;
    II- élimination des impuretés de la surface du composant suite au processus de production par dégraissage chimique de la surface;
    III- élimination de l'hydroxyde de magnésium de la surface du composant par décapage de la surface;
    IV- activer une première fois la surface du composant générant du fluorure de magnésium en surface;
    V- uniformiser la surface du composant par gravure de la surface;
    VI- activer une seconde fois la surface du composant générant du fluorure de magnésium en surface;
    dans lequel le procédé comprend au moins une étape de rinçage de la surface du composant avec de l'eau entre deux étapes consécutives du procédé, pour éliminer les résidus laissés sur la surface du composant de l'étape précédente.
  2. Procédé selon la revendication 1, dans lequel l'eau de l'étape de rinçage entre les étapes II et III contient des sels minéraux, tandis que l'eau entre les autres couples d'étapes consécutives est déminéralisée.
  3. Procédé selon les revendications 1 ou 2, dans lequel une finition superficielle du composant par une substance alcaline est prévue entre les étapes I et II.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le dégraissage chimique comprend l'étape d'immersion du composant dans un bain agité contenant de l'eau, au moins un sel et un tensioactif.
  5. Procédé selon l'une quelconque des revendications précédentes, comprenant, entre l'étape II et l'étape III, de laisser couler de l'eau avec des sels minéraux à la surface du composant dans au moins deux cuves séparées ou dans une seule cuve à renouvellement d'eau continu, pendant une durée inférieure à 15 minutes.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'étape III comprend l'immersion du composant dans un bain agité à température ambiante contenant 80-100 g/l de sels de fluorure et 60-110 ml/l d'acide sulfurique (H2SO4) ou 60-110 ml/l d'acide phosphorique (H3PO4).
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel à l'étape IV et à l'étape VI, le fluorure de magnésium (MgF2) est généré entre les phases α primaire, α eutectique et β des structures cristallines de l'alliage de magnésium.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'étape de rinçage du composant entre les étapes IV et V ou entre les étapes V et VI a lieu dans un bain agité avec de l'air ou ultrasons dans lequel le composant est immergé pendant moins de 90 secondes.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel à l'étape V le composant est immergé dans un bain à une température comprise entre 75 ° C et 85 ° C, et contenant 30-50 g/l de sels de pyrophosphate, 30- 50 g/l de sels de nitrate.
  10. Procédé selon la revendication précédente, dans lequel le bain est agité mécaniquement et constamment nettoyé par un système de filtration.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel, après l'étape VI, le procédé comprend l'étape supplémentaire de rinçage de la surface du composant pendant moins de 90 secondes avec de l'eau déminéralisée dans un bain agité pour éliminer les résidus de la surface du composant laissés par l'étape précédente du processus.
  12. Procédé selon la revendication 11, comprenant l'étape d'uniformiser une seconde fois la surface du composant par gravure de la surface.
  13. Procédé de nickelage autocatalytique comprenant l'étape de:
    - traiter une surface d'un composant en alliage de magnésium selon un procédé selon l'une quelconque des revendications précédentes;
    - nickelage autocatalytique de la surface du composant en l'immergeant dans un bain alcalin contenant du nickel.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage de magnésium est choisi parmi les types d'alliages suivants: AZ91, AZ31, AZ21, AM50, AM60, ZK30 ou ZK60.
  15. Procédé selon l'une quelconque des revendications précédentes, dans lequel le procédé de fabrication est choisi parmi les suivants: extrusion, laminage, filière, moulage ou injection.
EP15709985.4A 2015-01-27 2015-01-27 Procédé de traitement de surface d'un alliage de magnésium et procédé de dépôt autocatalytique de nickel sur une surface traitée Active EP3294926B1 (fr)

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