EP1149185B1

EP1149185B1 - Ferrate conversion coatings for metal substrates

Info

Publication number: EP1149185B1
Application number: EP99966296A
Authority: EP
Inventors: Zoran Minevski; Cahit Eylem; Jason Maxey
Original assignee: LYNNTECH Inc
Current assignee: LYNNTECH Inc
Priority date: 1998-12-15
Filing date: 1999-12-15
Publication date: 2004-03-03
Anticipated expiration: 2019-12-15
Also published as: EP1149185A1; AU2188800A; ATE261003T1; DE69915372T2; DE69930163T2; ES2213403T3; DE69930163D1; ATE318943T1; DK1149185T3; DE69915372D1; AU2186800A; WO2000036182A1

Abstract

A method employing oxide film conversion coatings prepared using ferrate (VI) as the oxidizing agent is disclosed. Metal substrates or surfaces, such as aluminum, aluminum alloys or other metals, are contacted with an aqueous solution comprising ferrate (VI) anions to form a corrosion resistant conversion coating on the surface thereof. The ferrate anion concentration is preferably between about 0.0166 % and about 1.66 % by weight. The coating process is carried out by dipping, spraying, or painting at temperatures ranging from 25 DEG C to 100 DEG C for a period of time ranging from about 1 second to about 5 minutes.

Description

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a method for forming a conversion coating on metal surfaces or substrates.

Background of the Related Art

In general, chemical conversion coatings are formed chemically by causing the surface of the metal to be "converted" into a tightly adherent coating, where either all or part of the conversion coating consists of an oxidized form of the substrate metal. Chemical conversion coatings can provide high corrosion resistance to the substrate as well as strong bonding affinity for paint. The industrial application of paint to metals generally requires the use of a chemical conversion coating, particularly when the performance demands are high.

Although aluminum protects itself against corrosion by forming a natural oxide coating, the protection is not complete. In the presence of moisture and electrolytes, aluminum alloys, particularly aluminum alloys with a high copper content, corrode much more rapidly than pure aluminum.

In general, there are two types of processes for treating aluminum to form a beneficial conversion coating. The first is by anodic oxidation (anodization) in which the aluminum component is immersed in a chemical bath, such as a chromic or sulfuric acid bath, and an electric current is passed through the aluminum component and the chemical bath. The conversion coating formed on the surface of the aluminum component offers resistance to corrosion and a bonding surface for organic finishes.

The second type of process is by chemically producing a conversion coating, which is commonly referred to as a chemical conversion coating, by subjecting the aluminum component to a chemical solution, such as a chromic acid solution, but without using an electric current in the process. The chemical solution may be applied by immersion application, by manual application, or by spray application. The resulting conversion coating on the surface of the aluminum component offers resistance to corrosion and a bonding surface for organic finishes.

Chromate based conversion coatings have been widely used in applications where maximum corrosion protection is an issue. Immersion of aluminum or aluminum alloys in a chromate conversion coating bath results in a thick, corrosion resistant film consisting of hydrated Cr (III) and Al(III) oxides. The reaction is driven by reduction of the high valent Cr(VI) ion and oxidation of the Al metal. Some of the benefits of a chromate conversion coating include hydrophobicity and self-healing properties.

Many aluminum structural parts, as well as Cd plated, Zn plated, Zn-Ni plated, and steel parts, throughout the aircraft and aerospace industry are currently being treated using this chromic acid process technology. Chromic acid conversion films, as formed on aluminum substrates, have been shown to meet a 168-hour corrosion resistance criterion, but they primarily serve as a surface substrate for paint adhesion. Because of their relative thinness and low coating weights (40-150 milligrams/ft²), chromic acid conversion coatings do not reduce the fatigue life of the aluminum structure.

However, environmental regulations in the United States, particularly in California, and in other countries are drastically reducing the levels of hexavalent chromium compounds permitted in effluents and emissions from metal finishing processes. Accordingly, chemical conversion coating processes employing hexavalent chromium compounds need to be replaced.

Some of the most investigated non-chromate conversion coatings used in treatment of aluminum alloy-based materials are described below.

Sol-Gel technology uses polymers or metal oxides either alone or mixed to form complexes by the hydrolysis of appropriate precursor compounds. Sol-Gels can form powders or thin films that inhibit corrosion on substrates.

Fluorozirconium coating technology uses complexed transition metal salts to create a thin film on a substrate material similar to a conversion coating. Specifically, zirconium is mixed with fluorine to create fluorozirconium, which reacts with the part surface to form a coating.

Cobalt-based coatings use cobalt and molybdenum to treat substrate materials. The coatings created are low in electrical resistance and are good for corrosion resistance.

Rare Earth Metal (REM) salts may be applied by heated immersion to create protective layers on substrate materials. REMs provide corrosion resistance by producing a protective oxide film.

Potassium permanganate solutions can be used to create manganese oxide films on substrates. Manganese oxide films resulting from potassium permanganate treatment closely match the corrosion resistance of traditional chromic oxide films used in conversion coatings. Potassium permanganate coatings are very effective in protecting aluminum alloys.

Fluotitanic coatings, deposited from acid solutions with organic polymers, require few process steps, and can usually be done at ambient temperatures. Although these coatings have been widely used in a variety of applications, they have not been used in the aerospace industry.

Talc coatings, which are typically applied to aluminum substrates, are resistant to corrosion. These polycrystalline coatings are applied by precipitating aluminum-lithium compounds and other anions in an alkaline salt solution.

Anodizing is a process in which a metal surface is converted to an oxide layer, producing a tough, adherent surface layer. A thick oxide layer can be produced by immersing a part in an electrolytic solution and passing an electrical current through it, similar to electroplating. Then, by placing the part in boiling water, the film's pores can be sealed. As a result, the oxide changes from one form to another.

Despite these alternatives, there is a continuing need for a conversion coating solution that will form a stable, corrosion-resistant conversion coating on metal surfaces without containing or producing toxic chemicals. There is also a need for a conversion coating solution that provides enhanced corrosion protection on a variety of substrate materials and under a variety of conditions. Additionally, it would be desirable if the conversion coating provided a suitable surface for receiving organic coatings or paints.

US-A-2,850,416 discloses a composition and process for treating metals, such as steel or aluminium, using a solution containing 0.5-5% ferrate (VI) and having a pH of 7-11. The solution contains preferably sodium salts as a buffer or stabiliser.

FR-A-616,849 discloses a composition and process for treating ferrous metals using a solution containing NaOH, Na₂CO₃, PbO₂ and Na₂FeO₄.

According to one aspect of this invention there is provided a solution for forming a conversion coating on a metal surface, the solution comprising ferrate (V1) (FeO₄ ^2-) anions having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and combinations thereof and wherein the solution has a pH greater than 13.5.

According to another aspect of this invention there is provided a solution for forming a conversion coating on a metal surface, the solution comprising ferrate (V1) (FeO₄ ^2-) anions having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and combinations thereof and wherein the solution has a pH between 13 and 13.5.

Preferably the solution further comprises one or more additional oxidising agents selected from the group consisting of peroxide, hypochlorite, ozone and combinations thereof.

Advantageously the ferrate (VI) oxyanion is provided by a compound selected from a sodium ferrate (VI) salt, a potassium ferrate (VI) salt, a solution of ferrate (VI) in potassium hydroxide, a solution of ferrate (VI) in sodium hydroxide and mixtures thereof.

Preferably the solution further comprises ethylenediaminetetraacetic acid.

Advantageously the solution further comprises a salt selected from an alkali metal, or an alkaline earth metal, nitrate, chloride, fluoride or combinations thereof.

The invention also relates to a method for treating a metal surface, comprising cleaning and deoxidising the metal surface, rinsing the deoxidising metal surface with water, contacting the deoxidised and rinsing metal surface with an aqueous oxidising solution at a temperature in the range of 25-100°C, allowing the metal surface to be oxidised by the oxidising solution, and removing the oxidised metal surface from being in contact with the solution, characterised in that the oxidising solution is an aqueous solution comprising ferrate (VI) (FeO₄ ^2-) having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and, combinations thereof and wherein the solution has a pH greater than 13.5.

In another aspect the invention provides a method for treating a metal surface, comprising cleaning and deoxidising the metal surface, rinsing the deoxidising metal surface with water, contacting the deoxidised and rinsing metal surface with an aqueous oxidising solution at a temperature in the range of 25-100°C, allowing the metal surface to be oxidised by the oxidising solution, and removing the oxidised metal surface from being in contact with the solution, characterised in that the oxidising solution is an aqueous solution comprising ferrate (VI) (FeO₄ ^2-) having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and, combinations thereof and wherein the solution has a pH between 13 and 13.5.

Conveniently the ferrate (VI) is selected from a sodium ferrate (VI) salt, a potassium ferrate (VI) salt, a solution of ferrate (VI) in potassium hydroxide, a solution of ferrate (VI) in sodium hydroxide and mixtures thereof.

Advantageously the metal surface is selected from aluminium, aluminium alloy, steel or other ferrous metals.

Preferably the solution further comprises a salt selected from an alkali metal, or an alkaline earth metal, nitrate, chloride, fluoride or combinations thereof.

Conveniently the metal surfaces contacted with the oxidising solution for between 1 second and 5 minutes.

Advantageously the ferrate solution has a transition metal oxyanion concentration between 0.1% and 5% by weight.

Preferably the aqueous oxyanion solution further comprises one or more additional oxidising agents selected from peroxide, hypochlorite, ozone and combinations thereof.

Conveniently the aqueous solution further comprises ethylenediaminetetraacetic acid.

The method may additionally comprise the step of contacting the oxidised metal surface with a post treatment solution containing one or more compounds selected from an alkaline metal silicate, an alkali metal borate, an alkali metal phosphate or mixtures thereof to provide an oxide film conversion coating.

The method may further comprise contacting the oxide film conversion coating with lithium nitrate.

The method may additionally comprise contacting the oxide film conversion coating with calcium hydroxide.

Optionally the method may further comprise the steps of cleaning the metal surface prior to contacting the metal surface with ferrate solution and / or exposing the cleaned metal surface to boiling water or anodisation to form an oxide or hydrous oxide layer.

It is also optional to contact the conversion coating surface formed by ferrate oxidation with a post treatment solution containing one or more compounds selected from an alkali metal silicate, an alkali metal borate, an alkali metal phosphate, lithium nitrate, magnesium hydroxide, calcium hydroxide, barium hydroxide or mixtures thereof. Preferably, the concentration of the one or more compounds is between about 0.015% and about 5% by weight. If calcium hydroxide is used, the preferred concentration is between about 0.06% and about 0.09% by weight and, preferably, the solution is prepared in water in the absence of carbon dioxide. The post treatment is preferably conducted at a solution temperature between about 10°C and about 100°C for a period of between about 1 minute and about 20 minutes.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the above recited features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarised above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Figure 1 is a graph showing salt fog survival of conversion coatings prepared with at two ferrate concentrations without oxyanions, with molybdate, with permangnate, and with both molybdate and permanganate.

Figure 2 is a table showing salt fog survival of ferrate conversion coatings prepared from various ferrate solutions with and without pre-treatment steps or post-sealing steps.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a conversion coating process that forms a stable and corrosion-resistant oxide film on the surface of metal substrates using ferrate (V1) as the oxidising agent. The conversion coating process uses an aqueous solution comprising ferrate anions, preferably having a ferrate anion concentration between 1 millimolar (about 0.0166% by weight) and 100 millimolar (about 1.66% by weight). The solution also includes one or more transition metal oxyanions that form stable metal oxides in the coatings and act as inhibitors to corrosion of the coated metal. The transition metal oxyanions are selected from permanganate, molybdate, vanadate, tungstanate, or combinations thereof, preferably at a concentration between about 0.1% and about 5% by weight. The coating process is carried out at temperatures ranging between 25°C and 100°C, and a contact time ranging between 1 second and 5 minutes. The conversion coating maybe produced on various metal surfaces or substrates, including but not limited to aluminium, aluminium alloys, steels (e.g. carbon steels and stainless steels), and other ferrous metals. The pH of the ferrate solution is 13 - 13.5 or greater than 13.5.

Optionally, yet preferably, the surface of the metal substrate is pre-treated before being contacted with the aqueous ferrate solution. Most preferably, the metal surface is cleaned by sonicating in acetone for 30 minutes, then cleaned in an alkaline solution. The cleaned metal surface may then be immersed in a deoxidising solution such as LNC deoxidiser (Oakite Products Inc., Berkeley Heights, New Jersey) to remove any residual oxide film from the metal surface. If the metal is aluminium or an aluminium alloy, the cleaned surface may then be exposed to boiling water or anodisation to form an oxide layer.

Furthermore, the invention may include an optional post-treatment process for the conversion coating. After the metal surface has been oxidised with a ferrate-containing conversion coating solution, the conversion coating can then be sealed with a post-treatment solution containing a sealant selected from an alkali metal silicate, an alkali metal borate, an alkali metal phosphate, lithium nitrate, magnesium hydroxide, calcium hydroxide, or barium hydroxide, with the most preferred sealant being calcium hydroxide. The preferred conditions for the post-treatment include a sealant concentration between about 0.015% and about 5% by weight, a solution temperature between about 10°C to about 100°C, and a contact time between about 1 minute and about 20 minutes. If calcium hydroxide is used, the post-treatment solution most preferably contains between about 0.06% and about 0.09% by weight calcium hydroxide and is prepared with water having a reduced carbon dioxide concentration.

The post-treatment step, for example using calcium hydroxide, is performed by reducing the concentration of carbon dioxide in water, forming a solution by combining calcium hydroxide with the water having a reduced concentration of carbon dioxide, and providing contact between the metal surface and the solution. The concentration of carbon dioxide in water may be reduced through any known process, but is preferably reduced by heating the water, most preferably to a temperature between 50°C and 100°C. Other processes for reducing the carbon dioxide concentration in water include passing the water through an electroosmotic pump, passing the carbon dioxide through a hydrophobic membrane, use of carbon dioxide scavengers or centrifuging the water. It is important that the carbon dioxide content of the water be reduced, since the amount of carbon dioxide present in water at room temperature will yield a solution that does not produce the desired conversion coating.

Aluminium or other substrate panels prepared with ferrate conversion coatings are immersed in one or more post-treatment solutions, such as alkali metal silicate and calcium hydroxide, between 80°C to 100°C for 1 minute to 20 minutes. Preferably, the treated aluminium panels receive post-treatment by being immersed, first in an aqueous solution containing 0.09% by weight calcium hydroxide and 0.6% by weight lithium nitrate at 100°C for 20 minutes, and second in an aqueous solution containing 2.4% by weight alkali metal silicate at 80°C for 2 minutes. Optionally, the aqueous calcium hydroxide solution may further include manganese, molybdenum or a combination thereof that form stable metal oxides in the coatings and act as inhibitors to corrosion of the coatings.

The present invention provides a method that can be used to coat metal substrates with a non-toxic oxide film conversion coating that exhibits corrosion resistance comparable to chromate conversion coatings. Ferrate contains iron in a +6 oxidation state (Fe⁶⁺) and is thus quite useful as a powerful oxidising agent. Suitable forms of ferrate include, but are not limited to, sodium ferrate salts, potassium ferrate salts, solutions of ferrate in potassium hydroxide, solutions of ferrate in sodium hydroxide, and mixtures thereof.

Ferrate (VI) for use in the solution of the present invention can be prepared in a number of ways. The ferrate (VI) anion can be produced by providing an aqueous solution of iron nitrate complexed with ethylenediaminetetraacetic acid, and hydroxide ions. A strong oxidising agent, such as hydrogen peroxide, is then added to the solution to oxidise the iron (III) to ferrate (VI).

Ferrate may also be produced by electrochemical methods. Generally, iron metal can be used as the anode with a cathode made from carbon, nickel or other suitable material. In an alkaline solution, a current is applied across the anode and cathode which results in the oxidation of iron, from either an iron compound in the anolyte or the anode itself, to ferrate (VI). Large volumes of relatively high concentration ferrate (VI) can be produced by this method. The ferrate may then be precipitated to produce solid ferrate salts, or the solution can be used as a source of ferrate.

Optionally, the aqueous ferrate solution may include an alkali metal salt or an alkaline earth metal salt as an accelerator, activator, or passivator of the conversion coating reaction. Suitable alkali metal salts or alkaline earth metal salts include but are not limited to nitrates, chlorides and fluorides, preferably lithium nitrate, lithium chloride, and sodium nitrate. The preferred alkali metal salt concentration is between about 0.1 % and about 5.0% by weight.

Optionally, the aqueous ferrate solution may be stabilised by adding one or more additional oxidising agents or ethylenediaminetetraacetic acid to the ferrate solution. Additional oxidising agents may be selected from peroxides, hypochlorite and ozone. The concentration of the additional oxidising agents is preferably between about 0.1% to about 0.5% by weight. The presence of other oxidising agents maintains the iron in the ferrate solution in a +6 oxidation state.

Example 1. Preparation of aluminium or aluminium alloy panels (Comparative Example)

Except where indicated, aluminium or aluminium alloy panels were used in the following examples. Prior to contacting the panels with a coating solution, the panels were prepared by sonication in acetone for 30 minutes. They were then cleaned with an alkaline cleaning solution (such as 4215 NCLT available from Elf Atochem - Turco Products Division, Westminster, California) for 10 minutes at 50°C to 60°C. The panels were then rinsed with deionised water and immersed in a deoxidising solution of 15% LNC deoxidiser (Oakite Products, Inc., Berkeley Heights, New Jersey) for 10 minutes at room temperature. Optionally, the cleaned panels could then be exposed to boiling water or anodisation to form an oxide layer. The panels were then thoroughly rinsed with deionised water and allowed to dry.

Example 2. Aluminium or aluminium alloy panels treated with conversion coating solutions containing ferrate (VI) in combination with one or more oxyanions or salts.

Aqueous solutions of ferrate (VI) having concentrations between 0.0166% (1 mM) and 1.66% (100 mM) ferrate (VI), with or without 0.5% sodium nitrate, 1.0% to 3.0% of one or more of lithium chloride or lithium nitrate were prepared. The aluminium panels prepared as described in Example 1 were immersed in this conversion coating solution for between 1 second and 5 minutes at temperatures between 25°C and 80°C. the panels were then rinsed thoroughly with deionised water, dried in air for 48 to 94 hours, and tested by salt fog spray according to ASTYM B-117 test method (samples were placed at 15° angle).

Example 3. Aluminium or aluminium alloy panels treated with conversion coating solutions containing ferrate (VI) and EDTA at low hydroxide concentrations in combination with one or more oxyanions or salts

Aqueous solutions of ferrate (VI) with EDTA having concentrations between 0.0166% to 1.66% ferrate (VI) at a pH between 13 and 13.5 were prepared. The solutions could also contained 1.0% to 3.0% of one or more of potassium permanganate and potassium molybdate, and 0.5% to 1.0% of one or more of lithium chloride, lithium nitrate, of sodium nitrate. Aluminium panels prepare as described in Example 1, were immersed in this conversion coating solutions for between 1 second and 10 minutes at temperatures between 25°C and 80°C. The panels were then rinsed thoroughly with deionised water, dried in air for 48 to 94 hours, and tested by salt fog spray according to the ASTM B-117 test method (samples were placed at 15° angle).

Example 4. Aluminium or aluminium alloy panels treated with conversion coating solutions containing only ferrate (VI) and then treated with post-sealants. (Comparative Example)

Aqueous solutions of ferrate (VI) having concentrations ranging between 3 - 80 mmol/l ferrate (VI) were prepared. Aluminium panels, prepared as described in Example 1, were immersed in each of the solutions for periods ranging from 1 second to 5 minutes at a temperature ranging between 25°C and 80°C. The treated aluminium panels then received post-treatment by being immersed, first in an aqueous solution containing 0.09% by weight calcium hydroxide and 0.6% by weight lithium nitrate at 100°C for 20 minutes, and second in an aqueous solution containing 2.4% by weight alkali metal silicate at 80°C for 2 minutes. The panels were then rinsed thoroughly with deionised water, dried in air for 48 to 94 hours, and tested by salt fog spray according to the ASTM B-117 test method (samples were placed at 15° angle).

Example 5. Aluminium or aluminium alloy panels treated with conversion coating solutions containing ferrate (VI) in combination with one or more oxyanions or salt and then treated with post-sealants.

Aqueous solutions of ferrate (VI) having concentrations between 3.10 mmol/l ferrate (VI), with or without 0.5% sodium nitrate, 1.0% to 3.0% of one or more of potassium permanganate and potassium molybdate, and 0.5% to 1.0% of one or more of lithium chloride or lithium nitrate were prepared. The aluminium panels prepared as described in Example 1 were immersed in this conversion coating solution for between 1 second and 5 minutes at temperatures between 25°C and 80°C. The treated aluminium panels then received post-treatment by being immersed, first in an aqueous solution containing 0.09% by weight calcium hydroxide and 0.6% by weight lithium nitrate at 100°C for 20 minutes, and second in an aqueous solution containing 2.4% by weight alkali metal silicate at 80°C for 2 minutes. The panels were then rinsed thoroughly with deionised water, dried in air for 48 to 94 hours, and tested by salt fog spray according to the ASTM B-117 test method (samples were placed at 15° angle).

Example 6. Aluminium or aluminium alloy panels treated with conversion coating solutions containing ferrate (VI) and EDTA at low hydroxide concentrations in combination with one or more oxyanions or salts and then treated with post-sealants.

Aqueous solutions of ferrate (VI) with EDTA having concentrations between 0.0166% to 1.66% ferrate (VI) at pH between 13 and 13.5 were prepared. The solutions could also contained 1.0% to 3.0% of one or more of potassium permanganate and potassium molybdate, and 0.5% to 1.0% of one or more of lithium chloride, lithium nitrate, of sodium nitrate. Aluminium panels prepared as described in Example 1, were immersed in this conversion coating solutions for between 1 second to 5 minutes at temperatures between 25°C and 80°C. The treated aluminium panels were then immersed in one or more post-treatment solutions, such as alkali metal silicate and calcium hydroxide, between 80°C and 100°C for 1 minute to 20 minutes. The panels were then rinsed thoroughly with deionised water, dried in air for 48 to 94 hours, and tested by salt fog spray according to the ASTM B-117 test method (samples were placed at 15° angle).

Example 7. Stabilisation of ferrate (VI) in the conversion coating solution

The ferrate (VI) anions in the conversion coating solution may be stabilised by the addition of oxidisers such as peroxides, hypochlorites, ozone, or other oxidisers. The concentrations of these oxidisers can be varied between 0.1% and 0.5% by weight.

Claims

A solution for forming a conversion coating on a metal surface, the solution comprising ferrate (V1) (FeO₄ ^2-) anions having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and combinations thereof and wherein the solution has a pH greater than 13.5.
A solution for forming a conversion coating on a metal surface, the solution comprising ferrate (V1) (FeO₄ ^2-) anions having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and combinations thereof and wherein the solution has a pH between 13 and 13.5.
The solution of Claim 1 or 2 further comprising one or more additional oxidising agents selected from the group consisting of peroxide, hypochlorite, ozone and combinations thereof.
The solution of Claim 1, 2 or 3 wherein the ferrate (VI) oxyanion is provided by a compound selected from a sodium ferrate (VI) salt, a potassium ferrate (VI) salt, a solution of ferrate (VI) in potassium hydroxide, a solution of ferrate (VI) in sodium hydroxide and mixtures thereof.
The solution of any one of Claims 1 to 4 further comprising ethylenediaminetetraacetic acid.
The solution of any one of Claims 1 to 5 further comprising a salt selected from an alkali metal, or an alkaline earth metal, nitrate, chloride, fluoride or combinations thereof.
A method for treating a metal surface, comprising cleaning and deoxidising the metal surface, rinsing the deoxidising metal surface with water, contacting the deoxidised and rinsing metal surface with an aqueous oxidising solution at a temperature in the range of 25-100°C, allowing the metal surface to be oxidised by the oxidising solution, and removing the oxidised metal surface from being in contact with the solution, characterised in that the oxidising solution is an aqueous solution comprising ferrate (VI) (FeO₄ ^2-) having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and, combinations thereof and wherein the solution has a pH greater than 13.5.
A method for treating a metal surface, comprising cleaning and deoxidising the metal surface, rinsing the deoxidising metal surface with water, contacting the deoxidised and rinsing metal surface with an aqueous oxidising solution at a temperature in the range of 25-100°C, allowing the metal surface to be oxidised by the oxidising solution, and removing the oxidised metal surface from being in contact with the solution, characterised in that the oxidising solution is an aqueous solution comprising ferrate (VI) (FeO₄ ^2-) having a concentration of 1-100 mmol/l and one or more transition metal oxyanions selected from the group consisting of permanganate, molybdate, vanadate, tungstate and, combinations thereof and wherein the solution has a pH between 13 and 13.5.
The method of Claim 7 or 8 wherein the ferrate (VI) is selected from a sodium ferrate (VI) salt, a potassium ferrate (VI) salt, a solution of ferrate (VI) in potassium hydroxide, a solution of ferrate (VI) in sodium hydroxide and mixtures thereof.
The method of Claim 7, 8 or 9 wherein the metal surface is selected from aluminium, aluminium alloy, steel or other ferrous metals.
The method of any one of Claims 7 to 10 wherein the solution further comprises a salt selected from an alkali metal, or an alkaline earth metal, nitrate, chloride, fluoride or combinations thereof.
The method of any one Claims 7 to 11 wherein the metal surfaces are contacted with the oxidising solution for between 1 second and 5 minutes.
The method of any one of Claims 7 to 12 wherein the ferrate solution has a transition metal oxyanion concentration between 0.1% and 5% by weight.
A method of any one of Claims 7 to 13 wherein the aqueous oxyanion solution further comprises one or more additional oxidising agents selected from peroxide, hypochlorite, ozone and combinations thereof.
The method of any one of Claims 7 to 14 wherein the aqueous solution further comprises ethylenediaminetetraacetic acid.
The method of any one of Claims 7 to 15 comprising the step of contacting the oxidised metal surface with a post treatment solution containing one or more compounds selected from an alkaline metal silicate, an alkali metal borate, an alkali metal phosphate or mixtures thereof to provide an oxide film conversion coating.
The method of Claim 16 further comprising contacting the oxide film conversion coating with lithium nitrate.
The method of Claim 16 or 17 further comprising contacting the oxide film conversion coating with calcium hydroxide.