WO1999002759A1 - Procede de scellement pour substrats en metal et/ou en metal anodise - Google Patents

Procede de scellement pour substrats en metal et/ou en metal anodise Download PDF

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Publication number
WO1999002759A1
WO1999002759A1 PCT/NZ1998/000097 NZ9800097W WO9902759A1 WO 1999002759 A1 WO1999002759 A1 WO 1999002759A1 NZ 9800097 W NZ9800097 W NZ 9800097W WO 9902759 A1 WO9902759 A1 WO 9902759A1
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WO
WIPO (PCT)
Prior art keywords
anodised
magnesium
article
metal
acid
Prior art date
Application number
PCT/NZ1998/000097
Other languages
English (en)
Inventor
John Arnold Macculoch
Philip Nicholas Ross
Original Assignee
Magnesium Technology Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Magnesium Technology Limited filed Critical Magnesium Technology Limited
Priority to EP98932651A priority Critical patent/EP1017879A1/fr
Priority to CA002296539A priority patent/CA2296539A1/fr
Priority to JP2000502247A priority patent/JP2001509549A/ja
Priority to AU82481/98A priority patent/AU8248198A/en
Publication of WO1999002759A1 publication Critical patent/WO1999002759A1/fr

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Classifications

    • 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
    • C25D11/30—Anodisation of magnesium or alloys based thereon

Definitions

  • the present invention relates to sealing procedures for metal and/or metal alloy substrates whether anodised or not but suitable in any event for anodised magnesium or magnesium alloy surfaces.
  • Anodised films may commonly comprise a porous layer of metal oxide. If the pore structure did not exist, the anodic film could not form to a significant thickness owing to electrical resistance and the barrier to ionic transport posed by the oxide. While the pore structure allows a useful thickness of film to form, it may in some circumstances be a disadvantageous feature, as corrosive species may migrate through the pores to the underlying base metal. Accordingly, it is often desirable to "seal" the pores. Such sealing implies an agent that either physically fills the pores and plugs them or an agent that reacts chemically with the oxide film causing a plug to form capping the pores.
  • Some anodisation processes result in highly irregular pore sizes and shapes as well as a broad distribution in both size and shape.
  • the pores do not usually result from solubility of the magnesium oxide in the electrolyte but from physical factors associated with the formation of the film during electrochemical oxidation.
  • Simple solutions such as immersion of the anodised surface in boiling water or a simple ionic salt do not result in a sealed film.
  • a successful method of sealing anodised magnesium articles requires the introduction of another species to physically plug the pores.
  • Such a species must be inert and resistant to ingress of pitting initiators such as chloride ions, and of course, moisture as the presence of even small amounts of moisture may lead to galvanic corrosion and accelerated attack of the magnesium substrate.
  • the sealing agent must also be firmly bonded to the anodic film, preferably by way of a chemical or strong physical bond and the seal, when applied must be chemically resistant.
  • the present invention consists in a method of sealing the or a surface of a material, an article, a component or an assembly (hereafter "article' , ), being an article having, at least in part, at least one of a metal surface, a metal alloy surface, an anodised metal surface, and an anodised metal alloy surface, said metal being an element selected from the group consisting of magnesium, - j - beryllium, titanium, zirconium, hafnium, zinc, and aluminium, which method at least includes the steps of
  • the resin suspension includes an aqueous phase and micelle formation is as a result of the dispersion of the resin in the water and the presence of reactive groups on the resin dissociate, with one ion going into the aqueous phase and the other staying with the resin.
  • a small charged micelle forms, the size of which depends on the charge, which in turn depends on the degree of dissociation which is dependent on the pH and conductivity of the aqueous phase.
  • the surface(s) after step (I) is substantially free of ionisable species (eg; alkalinity if metal is magnesium).
  • ionisable species eg; alkalinity if metal is magnesium.
  • said metal element is selected from the group consisting of magnesium or aluminium or alloys thereof or fabricated mixed structures thereof.
  • the metal element is magnesium.
  • said deactivating agents are selected those (eg; including acid or acids) from those which form a sparingly soluble or insoluble magnesium salt.
  • said acid or acids is or are selected from the group consisting of lactic acid, tartaric acid or hydrofluoric acid.
  • said resin suspension is one which upon curing will provide a polymer coating which, optionally, may include inclusions such as pigment(s), graphite, etc.
  • polymers examples include polyurethanes. acrylics, polyacrylomelamines and epoxies.
  • the resin suspension is one which includes water.
  • said polymer is a polyurethane and said resin suspension includes an isocyanate resin.
  • said resin suspension includes water, a blocked isocyanate resin and a source of -OH moieties selected from alcohols and glycols (eg; a glycol ether).
  • a source of -OH moieties selected from alcohols and glycols (eg; a glycol ether).
  • Preferably said subsequently allowing the cure and/or causing the cure of the coating on the surface(s) to provide the seal results from applying heat or a source of unblocking radiation to the coated surface(s).
  • the heating is to above 137°C.
  • the voltage caused to apply to such surface(s) is a cathodic voltage.
  • said cathodic voltage is applied in the form of a direct current with little or no alternating component.
  • said voltage caused to apply to such surface(s) is an anodic voltage provided the resin is configured to yield a negatively charged micelle.
  • the surface(s) is or are anodised, prior to such surface(s) being treated to a presence of a deactivating agent (eg; acid(s)).
  • a deactivating agent eg; acid(s)
  • the exposing of the surface(s) to the resin suspension is by means of dipping.
  • said washing step(s) may include exposure to a wetting agent.
  • said article is washed prior to treating to a presence of a deactivating agent (eg; of acid(s)). Such preliminary washing may include or may be followed by exposure to a wetting agent prior to the treating of the surface(s) to a presence of (eg) acid(s).
  • a deactivating agent eg; of acid(s)
  • said article also includes a surface or surfaces which is or are other than one of those of the metals or alloys specifically referred to.
  • the article is an assembly which includes a surface or surfaces (the same or different) having at least in addition, an aluminium or aluminium alloy content.
  • said aluminium or aluminium alloy content surface(s) have been anodised prior to the treating of the (anodised or un-anodised) said metal and'or said metal alloy surface(s) to the presence of acid(s).
  • the invention consists in a method of sealing the or a surface of a material, an article, a component or an assembly (hereafter "article"), being an article having, at least in part, at least one of a magnesium surface. a magnesium alloy surface, an anodised magnesium surface, and an anodised magnesium alloy surface, which method at least includes the steps of: if the article, at least in part, has an anodised surface, treating the anodised magnesium or magnesium alloy surface to a presence of an acid or acids not substantially destructive of the anodised surface and/or if the article, at least in part, has a non anodised magnesium or magnesium alloy surface, treating that surface to a presence of an acid or acids not substantially destructive of that surface, exposing the surface(s) to be sealed to an isocyanate resin suspension whilst a cathodic voltage is caused to apply to such surface(s), the surface(s) being substantially free of alkalinity prior to such exposure and the isocyanate resin suspension being such as to be
  • the invention consists in an article sealed by a process as previously setforth.
  • said article has, in addition to said (anodised and or un-anodised) metal and/or metal alloy surface(s), anodised and/or un-anodised surfaces of aluminium or of aluminium alloy content.
  • said article has a magnesium alloy surface high in aluminium content that has been un-anodised or anodised.
  • the invention consists in an article having a polymer sealed (anodised and/ or un-anodised) surface at least one region of which is of a polymer sealed metal surface, a metal alloy surface, an anodised metal surface, and/or an anodised metal alloy surface, said metal being an element selected from the group consisting of magnesium, beryllium, titanium, zirconium, hafnium, zinc and aluminium. and wherein said coating has been provided thereto [and, optionally, to other un-anodised and/or anodised surfaces of the article] by means of allowing the cure and or causing the cure of a coating of the uncured polymer reactants after exposing the surface!
  • the invention is a polyurethane (or other polymer) sealed (anodised and/or un-anodised) surface (preferably magnesium and/or magnesmm alloy surfaces).
  • Other surfaces in addition to be sealed may be metallic.
  • the invention consists in, m a process for sealing metal or metal alloy mate ⁇ als (preferably magnesium or magnesium containing) [anodised or unanodised], the use of a dilute HF solution and/or an acid fluo ⁇ de salt solution (eg NH F.HF) as a pretreatment of the surface to be sealed by a following electrophoretic process.
  • metal or metal alloy mate ⁇ als preferably magnesium or magnesium containing
  • an acid fluo ⁇ de salt solution eg NH F.HF
  • the present invention consists in a method of providing a polyurethane coating to a magnesium containing article comp ⁇ smg the steps of providing an emulsion having the polyme ⁇ sable requirements of a polyurethane;
  • said article is pretreated w ith a mildly acidic ⁇ nse followed by either a deiomsed water ⁇ nse or a ⁇ nse m dilute glycol ether solution
  • said cathodic voltage is in the range of at least 40 volts (eg, 40-70 volts)
  • said article is ⁇ nsed using a solvent bath and rinse aid p ⁇ or to cu ⁇ ng,
  • said article is d ⁇ ed and cured at approximately 180°C in preferably a blower oven.
  • a dye or opaque pigment is added to the polyurethane emulsion enabling the formation of a coloured polyurethane layer.
  • the invention also consists m an article thus coated. All % herein where the context allows are on a w/v basis.
  • Figure 1 is a flow diagram of a preferred procedure for sealing anodised or unanodised magnesium
  • FIG 2 is a flow diagram tying our proprietary magnesium or magnesium alloys (high or low magnesium content) anodising process described hereafter to the sealing process of Figure 1,
  • Figure 3 is a diagram of the use of a cathodic voltage regime in a process such as that of Figure 1 .
  • Figure 4 is a cross-section of a sealed anodic surface from a process of Figure 1 , showing optional pigment inclusions in the seal.
  • a seal process that is desc ⁇ bed herein provides a strong, firmly bonded and effective seal, being chemically inert and physically resistant to scratching, abrasion or cracking.
  • This process involves the application of a, as an example, polyurethane polymer by way of electrophoresis followed by a cure cycle.
  • the resulting seal provides a very high specification finish for magnesium articles.
  • the seal coating is preferably applied to a magnesium anodic film by way of the following steps (see also Figure 1 ):
  • the article is immersed in a deactivating solution preferably containing an acid, such acid being chosen so as not to attack the anodic film unduly while deactivating the surface of the magnesium alloy or anodised magnesium alloy.
  • a deactivating solution preferably containing an acid, such acid being chosen so as not to attack the anodic film unduly while deactivating the surface of the magnesium alloy or anodised magnesium alloy.
  • the article is commonly (optionally) prepared for subsequent processing by an immersion in a wetting agent.
  • the article is usually conditioned by a rinse in the aqueous phase of the electrophoretic process, which is sometimes a dilute aqueous solution of a glycol ether such as 1 -methoxy propan-2-ol.
  • the article is immersed in an emulsion comprising an aqueous phase and oil phase; the latter containing micelles of a blocked oligomer (ie; blocked polyurethane oligomer if the seal is to be a polyurethane).
  • the oil phase is preferably present to the extent of from 8 to 15% of the emulsion by weight, and contains a solvent which is commonly a longer chain glycol ether, such as hexoxy ethanol.
  • a voltage is applied to the anodised article, during which the charged micelles of resin are drawn towards its surface where they uncurl and deposit, forming a coating. This coating extends into the pores of any anodic films that might be present and throws uniformly over the surface of the part.
  • Such voltage may be either anodic or cathodic depending upon the characteristics of the resin micelles, but as commonly employed, the process is cathodic.
  • the electrophoretic process may involve (and will now be described by reference to) the application of a polyurethane film to the surface of the magnesium or magnesium alloy anodised part.
  • a polyurethane film may be deposited alone or together with other substances, whether these substances be dissolved or dispersed in the polymer micelles. Since other substances may be co-deposited, a variety of surface finishes may be obtained, and solvent based dyes or pigments may be added to the resin to yield a wide range of colours to the finished article.
  • the process is based on emulsion technology in that it comprises a dispersed mixture of two phases, one of which is aqueous while the other is immiscible with water and is based on a solvent, often a glycol ether solution.
  • the non- aqueous phase consists of tiny droplets which are dispersed throughout the aqueous phase.
  • the size of these droplets is critical to the success of the process and is controlled in part by regulating the pH of the emulsion.
  • the aqueous phase of the emulsion also often contains a glycol ether, but one which is miscible in water, such as 1 -methoxy propan-2-ol. This aids in the flow of the resin as it deposits on the surface of the substrate and ensures the layer builds up in an even and satisfactory manner.
  • the resin comprises an oligomer made up of various functional groups including at least one blocked isocyanate.
  • Isocyanate resins polymerise by cross-linking with alcohol groups to form smooth, even polyurethanes which are chemically resistant. These polyurethanes offer a range of favourable surface properties including wear resistance, abrasion resistance. UV absorption and favourable elastic properties.
  • polyurethane coatings are frequently chosen for heavy wear applications as for example on wooden floors where a shiny surface is required over time despite constant wear from use.
  • the blocking of the isocyanate prevents its crosslinking until a raised temperature, such as 137°C, is achieved. This occurs during the curing cycle. Once unblocked, a polyurethane cross-links very quickly.
  • the resin micelles must also carry an electrical charge as otherwise they would not be attracted to the cathode or anode and therefore not deposit on the surface of the substrate. They are given a charge by ensuring that the resin molecules have a number of ionic sites which in the emulsion form a water soluble negative or positive ion. leaving a nett charge of the opposite polarity within the micelle. In part this is a determinant of micelle size.
  • a water soluble organic acid ion is formed. Since this has a negative charge (R-COO ), it leaves behind a positive charge on the oligomer, commonly an amino group (R-NH 3 ⁇ ).
  • Preferred voltage applications include a DC voltage.
  • a voltage range of within 60 to 120 volts would be usual but not mandatory.
  • the resin molecules are oligomers which feature lengthy, hydrophobic chains of hydrophobic hydrocarbons, to which hydrophilic groups, such as sulphonate or amino are attached.
  • a droplet tends to form in which the hydrophobic parts of the molecule face inwards with the hydrophilic groups projecting outwards into the aqueous solution.
  • the droplet becomes electrically charged and due to this charge, it repels other droplets of resin.
  • a balance will be maintained where droplet size is dependent upon emulsion pH and the nature of the ionic sites present on the resin micelle.
  • the cathodic versions of this process will operate under acid conditions and the anodic versions under alkaline conditions.
  • the active, working emulsion is prepared from the base materials by a careful emulsification process.
  • the addition of water to the resin to prepare a suitable emulsion must be done slowly with adequate blending of the resin and water. That this is so stems from the fact that a fine, even dispersion of resin micelles is required and there is a tendency for insoluble organic materials to form large clumps rather than even dispersions.
  • solvents are miscible in each other and the resin is miscible in each, these may be blended with the resin prior to the commencement of the blending process with water.
  • Solvent dyes, or pigments added to produce a coloured film may also be added at this stage and blended with the resin as may other substances as discussed herein. In fact, such materials should be added prior to the addition of any water to ensure even and complete solution or dispersion within the desired phase.
  • a range of solvent-based dyes is soluble in organic solvents and these may be dissolved in the non-aqueous phase to yield a coloured deposited layer.
  • the layer deposited by means of the electrophoretic process is normally transparent, glossy and clear.
  • dye additions it is possible to create any desired colour. Since the dyes are transparent, however, the lightest shade possible is the base colour of the substrate and in cases where the substrate is itself coloured, either naturally or by means of a treatment carried out prior to sealing, an obvious limit on the range of possible colours results.
  • an opaque pigment may be added to the resin and blended with it. In this sense, the resin acts as a carrier for the pigment and deposits an opaque layer on the substrate surface.
  • the desired tone may be obtained by blending pigments. Typically brilliant white shades may be obtained by dispersions of titanium dioxide.
  • Pigments must be chemically unreactive and neutral in electrical charge. They may be blended with the resm before the preparation of an emulsion. Dyes must be blended with the resm p ⁇ or to the addition of any water since these are not soluble in water.
  • the resm provides a smooth, glossy finish While this satisfactory for many applications, a matt appearance may be desired It is possible to disperse species such as finely divided silica or mica into the resm to modify the surface appearance of the resm. Such a species must be chemically unreactive and incapable of lomsation as otherwise its presence would affect the delicate balance bet een the micelle size and the conductivity of the emulsion Such species must be blended with the resin p ⁇ or to their addition to the emulsion as otherwise their dispersion withm the non-aqueous phase of the emulsion becomes impossible
  • Silica may be added to provide a matt finish As the presence of an inert species such as this reduces the number of surface bonding sites a ⁇ ailable to the resm its concentration should not be so high that the strength ot the bond to the substrate is adversely affected. The gloss levels of the coating gradually decrease as more silica is dispersed into the resm
  • Mica may be added to give a metallic appearance similar to that of a metallic pamt This may be used in conjunction with pigments or other colou ⁇ ng agents to yield a va ⁇ ety of metallic pamt colours Again the addition of this species reduces the number of available sites within the resm micelles for surface bonding to the substrate.
  • a range of mate ⁇ als may be dispersed into the resm in this way, to give altered or enhanced surface properties when the resm is cured
  • the substances that are infused m this way may include but are not limited to pigments and inert fillers
  • a requirement of the process is that each candidate for infusion into the resm must be men and not able to promote the cross-linking of lsocyanates.
  • the dispersed species should be relatively close to the density of the resm otherwise there would be a tendency for it to fall out of the emulsion.
  • Metals which are generally subject to attack over time by bath constituents, particularly the mildly acidic cathodic resins, are not normally suitable as dispersed fillers.
  • a filler may be chosen to give the sealed film special properties.
  • the polyurethane film resulting from the normal application of the process is highly insulating. Infusion of electrically conductive carbon black may reduce this and even render the film conductive. Care must be taken to avoid an excess of carbon in the dispersion as this disrupts the ionisation and polarisation of the micelles which is so necessary for deposition on the part to be coated.
  • a problem in infusing such species into the resin micelles is that the stability of the resin is based on a fine balance, both chemically and electrically. Any materials that disrupt this balance may cause micelles to be attracted together, resulting in precipitation of sticky lumps of resin, or alternatively, some agents may even bring about the polymerisation of the resin. In general, the presence of an additional species within the resin micelles requires that continual agitation be employed to ensure the emulsion remains uniform.
  • the curing cycle normally involves heating the resin to a sufficiently high temperature so that the isocyanate radicals attached the polymer chains will unblock. These then cross-link, forming a long chain polyurethane polymer.
  • the process by which the resin is polymerised need not involve the direct application of heat, although in its most common form, it does.
  • Curing may also be achieved by using infra-red.
  • the curing time required depends upon the infra-red flux, the wavelength of the applied infra-red and the nature of the parts to be cured. In cases where the parts are dark in colour or highly reflective of infrared energy, the curing cycles might be quite short owing to surface heating of the resin. Anodised magnesium articles are generally matt in appearance and therefore curing times may be lengthy. A wavelength close to that of visible light is recommended for the most rapid cures, that is, a wavelength from 700 nanometres to 1,200 nanometres.
  • UV exposures within the photo-sensitive range of diazo and photopolymer materials used within the printing and graphic arts trades may be sufficient to unblock some blocking agents and one modification of the resin is designed to operate as a photoresist material, cured by ultraviolet in precisely this manner.
  • the photoresist agent may be employed in conjunction with a film positive which is drawn into close contact with the deposited resin. After an ultraviolet light exposure, the film is removed, leaving uncured resin in areas where the film was opaque. A suitable solvent, leaving no polymer in these places may then remove this, while other areas feature a hard, cured surface of polyurethane.
  • Its application to anodised magnesium substrates is as a method of masking, where it is desired to leave certain regions uncoated. Complex shapes may be masked this way where conventional techniques of masking that require the application of a tape or paint, are simply too labour intensive.
  • Magnesium metal tends to form a surface oxide layer which protects it from fiirther attack. Though this film is not as well defined as the film that protects aluminium, it prevents the metal from dissolving in water despite the favourable electrochemical potential. In aqueous solution, some dissolution of magnesium oxide occurs resulting in the formation of hydroxide ions. The solubility of magnesium hydroxide in water is about 0.1 milligrams per litre, but this is sufficient for magnesium to exhibit an alkaline reaction with water.
  • Anodised magnesium components manifest a surface layer which is predominantly magnesium oxide, or which contains a mixture of ingredients such as magnesium aluminate. It is our belief that a basic reaction with water results from hydrolysis therefore, regardless of the chemistry of the anodising process, the surface of the article is essentially alkaline.
  • the electrophoresis resin Since the electrophoresis resin is extremely dependent upon pH, as this regulates micelle size and ionic charge on the micelle, the surface must normally be made receptive to the resin micelle. Often a deactivation step is required to do this as otherwise the resin will not deposit co ⁇ ectly.
  • a magnesium article for example, when immersed without deactivation in Techniclad" HDXC resin, which is a cathodic electrophoretic resin, will tend to form a thick poorly adherent coating featuring spheres of coagulated resin. This is unusable and represents a failure of the process. If the surface is modified by reaction with a suitable acid, the surface alkalinit ' no longer exists and the resin deposits normally.
  • the acid must form a sparingly soluble or insoluble magnesium salt as otherwise the magnesium compound formed by reaction with the anodic film will wash off and the surface will still be alkaline by hydrolysis.
  • the acid should not substantially dissolve the anodic film during the films exposure to the acid(s).
  • Lactic acid for instance, forms magnesium lactate by surface reaction with either magnesium metal or the anodic film and is suitable, although excessive exposure to the acid will result in stripping of the anodic film from the metal substrate.
  • an acid which produces a soluble magnesium salt for instance, acetic acid
  • acetic acid merely dissolves the anodic film without producing a pH neutral film.
  • the use of acetic acid in an attempt to deactivate the surface is generally prone to failure for this reason. If any magnesium acetate is carried over into the resin bath, it tends to dissolve thereby creating an undesirable increase in the concentration of ions in the bath and as a consequence, the conductivity.
  • Stearic acid n-octyldecanoic acid
  • the acid does not react with either magnesium metal or magnesium oxide and no deactivation results.
  • Tartaric acid is a good combination of an acid that is sufficiently water soluble to react with the magnesium or magnesium oxide anodic film while providing an almost insoluble magnesium salt that then presents a deactivated surface to the resin micelles.
  • a problem inherent in deactivating the surface of the magnesium or anodised magnesium article is that the entire surface of the article must be treated.
  • Anodised magnesium features a highly porous structure and it is necessary for the acid to "wet out” the entire surface. Failure to penetrate recesses will result in unacceptable results from resin agglomeration and "cissing".
  • hydrofluoric acid forms magnesium fluoride, MgF ; , by reaction with either magnesium metal or magnesium oxide.
  • MgF magnesium fluoride
  • the magnesium fluoride is very insoluble in water and forms a stable, strongly adherent species, ideal for subsequent application of a seal. It may be employed to yield a high quality surface finish on either magnesium metal articles or anodised magnesium articles.
  • careful rinsing should be conducted after the immersion in hydrofluoric acid and prior to immersion in the aqueous phase of the electrophoretic process.
  • components comprising two or more different metals are to be coated. These components may feature magnesium or a magnesium alloy connected in some way to an aluminium alloy. Aluminium, while commonly anodised in sulphuric acid solutions, may be anodised in electrolytes used in some magnesium anodisation processes. The film is different in character to that normally obtained from sulphuric acid anodisation. Aluminium may be sealed using an electrophoretic process as described herein.
  • An anodised aluminium component may also be sealed by such means.
  • An article comprising a magnesium part bonded to an aluminium part may be anodised through the same process then sealed.
  • the anodic film covering the aluminium part is different in thickness to that covering the magnesium article.
  • Beryllium a metal used largely in military applications, may also be anodised using certain magnesium techniques (eg; our proprietary anodisation process) and then sealed using this technology.
  • Beryllium though the first member of Group II of the periodic table (in which magnesium also falls), exhibits much behaviour in common with aluminium (which is in Group III). As such, it exhibits amphoteric behaviour and it tends towards considerable covalency in its chemical compounds.
  • Figure 4 shows a cross-section of a sealed magnesium or magnesium alloy material in accordance with the present invention.
  • the metal or metal alloy substrate 1 is shown having an anodised surface 2 thereof which has been sealed with an appropriate polymer 3 which may optionally include pigment inclusions 4.
  • Figure 3 shows a preferred apparatus in accordance with the present invention in which
  • a magnesium alloy plate ( AZ91D) was anodised using our proprietary process, creating an anodic film 15 ⁇ m in thickness. This was deactivated in a solution of lactic acid, comprising 1% lactic acid (2-hydroxypropanoic acid) and 0.01% of a glycol-based wetting agent. The temperature of the deactivating bath was ambient (20°C) and the immersion time in the bath was 2 minutes. Following this, the plate was sealed using a cathodic voltage of 80 volts for 90 seconds, and on inspection it proved to have a uniform film which after curing in an infrared oven for 90 minutes was found to add an additional 15 ⁇ m to the overall film thickness.
  • Example 2 A magnesium alloy plate (AM50A) was anodised using our proprietary process, creating an anodic film that was found to be 24 ⁇ m in average thickness using an eddy current meter. This was deactivated in a bath containing 35% hydrofluoric acid for one minute, followed by a brief rinse in a dilute solution of sodium carbonate to neutralise all traces of acid. Another rinse, in deionised water, followed, then the plate was sealed in a cathodic bath using a potential of 1 10 volts for 90 seconds. The plate was found to exhibit a uniform layer of resin, and on testing following an oven cure at 180°C for 30 minutes, the combined thickness of the anodic film and seal was found to be 29 ⁇ m.
  • Example 3 A magnesium alloy plate (AM50A) was anodised using our proprietary process, creating an anodic film that was found to be 24 ⁇ m in average thickness using an eddy current meter. This was deactivated in a bath containing 35% hydrofluoric acid for one minute, followed by
  • a magnesium alloy plate (AM50A) was partially immersed in 35% hydrofluoric acid for one minute, during which time the surface appearance of the plate darkened slightly as magnesium fluoride formed on the exposed surface. The whole plate was then rinsed in sodium carbonate solution followed by a deionised water rinse. This was sealed using a cathodic process, at a potential of 60 volts for 80 seconds. The plate was found to exhibit a uniform layer of resin where deactivation had been effected by the hydrofluo ⁇ c acid, with an uneven deposit elsewhere. After curing, the portion of the plate which had been deactivated was found to have a shiny layer of seal of approximately 15 ⁇ m in thickness.
  • An anodised magnesium alloy plate (AZ91D) possessing a coating thickness of 15 ⁇ m was deactivated in a benzoic acid solution (0.2%) for twenty minutes.
  • a titanium clip was anodised, yielding a grey film having a thickness of approximately one micron.
  • Our proprietary anodising process was employed.
  • Example 6 A sheet of AZ3 IB alloy magnesium that had been hot rolled and extruded was prepared for anodising in our proprietary process by removal of surface dirt and imperfections in an etch bath containing 1.0 molar hydrochloric acid. This resulted in a vigorous effervescence as the etch removed surface metal. The sheet was then treated in the phosphate bath of our proprietary process and anodised to yield a film having a thickness of approximately 25 microns. This was immersed in a 0.5% solution of lactic acid for five minutes, following which it was sealed in a cathodic bath containing a matting agent (a modified silica) together with a mixture of a black and a white pigment. The resin deposit resulting from a cathodic potential of 90 volts and a time of approximately 80 seconds was grey in appearance and cured to yield a matt grey texture in the polyurethane film.
  • a matting agent a modified silica
  • a magnesium casting (AZ91 D alloy) was anodised to give a coating of around 20 microns using our proprietary process. This was then deactivated in a bath containing 0.5% lactic acid then sealed using a cathodic process to which black pigment had been added, together with a quantity of a blue-black solvent dye. The appearance of the emulsion was deep black in colour, and the resin deposit on the casting was also black in appearance. Upon curing the finished article exhibited a shiny black appearance.
  • Example 8 A magnesium plate, die-cast from AZ91D alloy, was anodised using our proprietary process to a coating thickness of 15 ⁇ m was deactivated in a lactic acid solution of approximately 0.5% lactic acid, for approximately one minute. The article was then sealed in a cathodic resin bath containing a white pigment dispersed into the resin. The article was sealed using a cathodic voltage of 60 volts and the appearance of the final article was glossy and a brilliant white colour.
  • a test plate comprising AZ91 D magnesium alloy was anodised to a thickness of 25 ⁇ m using our proprietary process then coloured using our proprietary colouring process described in our PCT/NZ98/00030, specifically a red vinyl sulphone reactive dye.
  • the coloured article was then introduced to a lactic acid solution containing 0.5% lactic acid whereupon there was a pronounced leaching of the colour.
  • the article was still coloured red, and this was sealed using a cathodic clear seal which was applied at a voltage of 60 volts for 80 seconds.
  • the final article had a glossy coat over the red substrate after curing for half an hour in a thermowave oven.
  • a magnesium alloy (AM50A) test plate was immersed in 1 % hydrofluoric acid for three minutes, during which time visible effervescence ceased. This plate was then rinsed in a dilute solution of sodium carbonate to eliminate any residual hydrofluoric acid carried out of the bath. The plate was rinsed thoroughly in deionised water then sealed using a cathodic process at 70 volts for 90 seconds. The result was a clear, uniform seal after an oven cure of 30 minutes at 180°C. The seal had a thickness of 16 ⁇ m.
  • Example 11 A magnesium alloy plate (AM50A) was anodised using our proprietary process, to a surface thickness of 25 microns. This was immersed in 1 % hydrofluoric acid for 90 seconds, rinsed in sodium carbonate solution and deionised water, then sealed using a cathodic process at 120 volts for 90 seconds. The result was a uniform clear seal after an oven cure at 180°C for 30 minutes. Following the application of the seal, the combined coating on the magnesium plate had a thickness of 33 ⁇ m.
  • An anodised magnesium alloy plate (AM50A) was anodised using our proprietary process to a surface thickness of 25 ⁇ m. This was immersed in a 1%
  • Example 13 A fabricated assembly comprising an extruded section of magnesium alloy AZ31B, a die casting of magnesium alloy AZ91D, aluminium sheet alloy 5005, aluminium extrusion alloy 6063, aluminium alloy 1350 (rod and wire), and aluminium casting alloy LM6 was anodised using our proprietary process.
  • the anodic film thickness was approximately 25 ⁇ m on the magnesium components and about lO ⁇ m on the aluminium sheet.
  • the resulting anodised assembly was then deactivated using a bath comprising 1% hydrofluoric acid. This was sealed using a cathodic polyurethane resin, operating at 1 10 V for 90 seconds. The result was a uniform clear, glossy seal having a thickness of approximately
  • Titanium Polyurethane Cathodic 1 % Lactic acid 1 ⁇ m Ano Goo ⁇ quality film
  • Tag denotes TAGNITE 8 , a registered trademark of Technology Applied Group, North Dakota, USA. This is a magnesium anodising process.
  • Magnetic denotes MAGOXID*, a registered trademark of AHC Oberflachentechnik, of Germany.
  • “Dow 17” refers to the process, Dow Number 17. as described in a publication of the Dow Chemical Company, USA. No thickness could be given for this anodising, as the coated part did not possess a flat profile so no measurement could be made. "Ano” is the coating of our proprietary anodised coating. In some cases the anodic film could not be assessed for thickness as the coated part possessed no flat faces. "MMC” refers to a magnesium MMC (ie; metal matrix composite) which in the specific instance contained 12% silicon carbide.
  • the zirconium alloy used comprised up to 4% hafnium, which is standard in all zirconium ores.
  • the hafnium has identical chemical properties to the zirconium and is not normally removed except for specialist applications such as fuel rod cladding in nuclear power reactors. No other alloying constituents were present.
  • the beryllium sample was pure beryllium metal with no included alloying constituents.
  • Aluminium alloys anodised Polyurethane Hydrofluoric acid or bifluonde salt (1 %) or metal (unanodised) cathodic

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé de scellement, par polymérisation, d'une surface anodisée ou non anodisée (en métal pur ou en alliage) renfermant au moins l'un des métaux suivants : magnésium, béryllium, titane, zirconium, hafnium, zinc et aluminium. Le procédé consiste à effectuer un traitement préliminaire par le biais d'un agent de désactivation (par exemple, acide fluorhydrique dans certains cas) pour rendre la surface à sceller sensiblement dépourvue de matériaux ionisables, puis à traiter par électrophorèse la surface désactivée au moyen d'une supension de résine pour établir un revêtement qui est ensuite polymérisé. Le procédé s'applique en particulier au magnésium et aux alliages à magnésium ainsi qu'aux structures à base de ce métal et de ses alliages renfermant par exemple de l'aluminium ou des alliages d'aluminium.
PCT/NZ1998/000097 1997-07-11 1998-07-09 Procede de scellement pour substrats en metal et/ou en metal anodise WO1999002759A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98932651A EP1017879A1 (fr) 1997-07-11 1998-07-09 Procede de scellement pour substrats en metal et/ou en metal anodise
CA002296539A CA2296539A1 (fr) 1997-07-11 1998-07-09 Procede de scellement pour substrats en metal et/ou en metal anodise
JP2000502247A JP2001509549A (ja) 1997-07-11 1998-07-09 金属及び／又は陽極処理した金属基板の封孔方法
AU82481/98A AU8248198A (en) 1997-07-11 1998-07-09 Sealing procedures for metal and/or anodised metal substrates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NZ32831697 1997-07-11
NZ328316 1997-07-11

Publications (1)

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WO1999002759A1 true WO1999002759A1 (fr) 1999-01-21

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EP (1) EP1017879A1 (fr)
JP (1) JP2001509549A (fr)
AU (1) AU8248198A (fr)
CA (1) CA2296539A1 (fr)
WO (1) WO1999002759A1 (fr)
ZA (1) ZA986096B (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000003069A1 (fr) * 1998-07-09 2000-01-20 Magnesium Technology Limited Procede pour boucher les pores de surfaces metalliques anodisees ou non
EP1302566A1 (fr) * 2001-10-11 2003-04-16 FRANZ Oberflächentechnik GmbH & Co KG Production d'une région de surface métalliquement conductive sur des alliages Al-Mg oxydés
US6777094B2 (en) 2001-06-28 2004-08-17 Alonim Holding Agricultural Cooperative Society Ltd. Treatment for improved magnesium surface corrosion-resistance
US6797147B2 (en) 2001-10-02 2004-09-28 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
DE102007007879A1 (de) 2007-02-14 2008-08-21 Gkss-Forschungszentrum Geesthacht Gmbh Beschichtung eines Bauteils
US7452454B2 (en) 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US7569132B2 (en) 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
DE102008009069A1 (de) 2008-02-13 2009-08-20 Gkss-Forschungszentrum Geesthacht Gmbh Beschichtung eines Magnesuimbauteils
US7578921B2 (en) 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
WO2010112914A1 (fr) 2009-04-03 2010-10-07 Keronite International Ltd Procédé de protection renforcée contre la corrosion de métaux de soupapes
EP2690203A1 (fr) * 2011-03-22 2014-01-29 Sumitomo Electric Industries, Ltd. Élément métallique et son procédé de fabrication
EP2693445A1 (fr) * 2012-08-02 2014-02-05 Nexans Procédé pour fabriquer un câble électrique comprenant une couche hydrophobe
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
CN108193252A (zh) * 2017-12-28 2018-06-22 西北稀有金属材料研究院宁夏有限公司 一种铍铝合金阳极氧化的新方法
TWI692549B (zh) * 2018-06-22 2020-05-01 美商惠普發展公司有限責任合夥企業 經陽極處理之金屬基板的無鎳密封技術
WO2020145951A1 (fr) * 2019-01-09 2020-07-16 Hewlett-Packard Development Company, L.P. Boîtiers destinés à des dispositifs électroniques
WO2020219061A1 (fr) * 2019-04-26 2020-10-29 Hewlett-Packard Development Company, L.P. Boîtiers de dispositif électronique ayant des bords chanfreinés
CN114959669A (zh) * 2022-05-18 2022-08-30 惠州市广麟材耀科技有限公司 热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜

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JP4367838B2 (ja) * 2002-03-25 2009-11-18 堀金属表面処理工業株式会社 導電性陽極酸化皮膜を表面に有するマグネシウム又はマグネシウム合金製品及びその製造方法
SG155111A1 (en) * 2008-02-26 2009-09-30 Kobe Steel Ltd Surface treatment material for semiconductor manufacturing system and method for producing same
CN103334143B (zh) * 2013-07-15 2016-01-20 湖南大学 一种锆合金表面快速制备耐磨氧化锆和氧化铝混合涂层的微弧氧化方法
JP2019119914A (ja) * 2018-01-09 2019-07-22 ジオネーション株式会社 樹脂ジルコニウム合金接合体及びその製造法
JP6787438B2 (ja) * 2019-04-25 2020-11-18 栗田工業株式会社 アルミニウム又はアルミニウム合金の陽極酸化処理面の封孔処理方法

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DE3825315A1 (de) * 1988-07-26 1989-08-03 Daimler Benz Ag Kraftfahrzeug mit einer innenausstattung, die in ihrer oberflaeche strukturierte ausstattungsteile und mit kunststoff verkleidete metallische ausstattungselemente aufweist
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000003069A1 (fr) * 1998-07-09 2000-01-20 Magnesium Technology Limited Procede pour boucher les pores de surfaces metalliques anodisees ou non
US7011719B2 (en) 2001-06-28 2006-03-14 Alonim Holding Agricultural Cooperative Society Ltd. Treatment for improved magnesium surface corrosion-resistance
US6777094B2 (en) 2001-06-28 2004-08-17 Alonim Holding Agricultural Cooperative Society Ltd. Treatment for improved magnesium surface corrosion-resistance
US6797147B2 (en) 2001-10-02 2004-09-28 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
US6916414B2 (en) 2001-10-02 2005-07-12 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
US8361630B2 (en) 2001-10-02 2013-01-29 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US9023481B2 (en) 2001-10-02 2015-05-05 Henkel Ag & Co. Kgaa Anodized coating over aluminum and aluminum alloy coated substrates and coated articles
US7452454B2 (en) 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US7569132B2 (en) 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US8663807B2 (en) 2001-10-02 2014-03-04 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating aluminum and/or titanium with ceramic oxides
US7578921B2 (en) 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
WO2003033778A1 (fr) * 2001-10-11 2003-04-24 FRANZ Oberflächentechnik GmbH & Co KG Production d'une zone superficielle a conduction metallique sur des alliages al-mg oxydes
EP1302566A1 (fr) * 2001-10-11 2003-04-16 FRANZ Oberflächentechnik GmbH & Co KG Production d'une région de surface métalliquement conductive sur des alliages Al-Mg oxydés
DE102007007879A1 (de) 2007-02-14 2008-08-21 Gkss-Forschungszentrum Geesthacht Gmbh Beschichtung eines Bauteils
EP1978052A1 (fr) 2007-02-14 2008-10-08 Gkss-Forschungszentrum Geesthacht Gmbh Revêtement d'un composant
EP2093308A1 (fr) 2008-02-13 2009-08-26 Gkss-Forschungszentrum Geesthacht Gmbh Revêtement d'un composant de magnésium
DE102008009069A1 (de) 2008-02-13 2009-08-20 Gkss-Forschungszentrum Geesthacht Gmbh Beschichtung eines Magnesuimbauteils
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
WO2010112914A1 (fr) 2009-04-03 2010-10-07 Keronite International Ltd Procédé de protection renforcée contre la corrosion de métaux de soupapes
EP2690203A1 (fr) * 2011-03-22 2014-01-29 Sumitomo Electric Industries, Ltd. Élément métallique et son procédé de fabrication
EP2690203A4 (fr) * 2011-03-22 2014-09-03 Sumitomo Electric Industries Élément métallique et son procédé de fabrication
EP2693445A1 (fr) * 2012-08-02 2014-02-05 Nexans Procédé pour fabriquer un câble électrique comprenant une couche hydrophobe
FR2994329A1 (fr) * 2012-08-02 2014-02-07 Nexans Procede pour fabriquer un cable electrique comprenant une couche hydrophobe
CN108193252A (zh) * 2017-12-28 2018-06-22 西北稀有金属材料研究院宁夏有限公司 一种铍铝合金阳极氧化的新方法
CN108193252B (zh) * 2017-12-28 2019-12-17 西北稀有金属材料研究院宁夏有限公司 一种铍铝合金阳极氧化的新方法
TWI692549B (zh) * 2018-06-22 2020-05-01 美商惠普發展公司有限責任合夥企業 經陽極處理之金屬基板的無鎳密封技術
WO2020145951A1 (fr) * 2019-01-09 2020-07-16 Hewlett-Packard Development Company, L.P. Boîtiers destinés à des dispositifs électroniques
WO2020219061A1 (fr) * 2019-04-26 2020-10-29 Hewlett-Packard Development Company, L.P. Boîtiers de dispositif électronique ayant des bords chanfreinés
CN114959669A (zh) * 2022-05-18 2022-08-30 惠州市广麟材耀科技有限公司 热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜

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AU8248198A (en) 1999-02-08
CA2296539A1 (fr) 1999-01-21
JP2001509549A (ja) 2001-07-24
EP1017879A1 (fr) 2000-07-12

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