Method of coating the surface of a metal substrate

Abstract

A method of coating the surface of a metal substrate includes a) applying a first composition on the surface of a metal substrate, the first composition being a solution comprising a liquid medium including sol-gel precursors of alcoxysilane type or of metallo-organic type; b) subjecting the first composition to first heat treatment to form an anchor layer on the metal substrate in which the sol-gel precursors are bonded to the metal substrate, a first temperature being imposed during the first heat treatment that is sufficient to eliminate all or part of the liquid medium and to encourage the bonding of the sol-gel precursors to the metal substrate; and c) applying a second composition on the anchor layer. The second composition includes coating compounds to obtain a coating on the anchor layer by forming bonds between the sol-gel precursors and the coating compounds.

Claims

1. A method of coating the surface of a metal substrate, the method comprising: a) applying a first composition on the surface of a metal substrate, the first composition being in the form of a solution comprising a liquid medium including sol-gel precursors of metallo-organic type, said sol-gel precursors being suitable for bonding with the metal substrate, wherein the metallo-organic type sol-gel precursors present the following general formula when the sol-gel precursors are in a non-hydrolyzed state and in a monomer state: Me(OOCR)nXm, in which Me is iron, R is an alkyl group, and when there is a plurality of groups R, each group R is an alkyl group, X is a group bound to the iron, and m and n are integers, n is greater than or equal to 1, m is greater than or equal to 0, and the sum m+n is equal to a valence of the iron, and wherein no step of pickling the surface of the metal substrate is performed before step a); b) subjecting the first composition to a first heat treatment so as to form an anchor layer on the metal substrate in which the sol-gel precursors are bonded to the metal substrate, a first temperature being imposed during the first heat treatment that is sufficient to eliminate all or part of the liquid medium and to encourage the bonding of the sol-gel precursors to the metal substrate, the first heat treatment being configured to avoid complete condensation among the sol-gel precursors; and c) applying a second composition on the anchor layer, the second composition including coating compounds so as to obtain a coating on the anchor layer by forming bonds between the sol-gel precursors and the coating compounds.

2. The method according to claim 1, wherein each of the sol-gel precursors of metallo-organic type has at least one ligand organic function suitable for bonding to the metal substrate, the ligand organic function including at least one of the following ligand groups: alcoxyl; amine; acryloxy; methacryloxy; dimethyl prosphate; diethyl phosphate; epoxy; and vinyl.

3. The method according to claim 2, wherein the sol-gel precursors of metallo-organic type are iron propionate or iron butyrate.

4. The method according to claim 1, wherein the coating compounds are selected from the following compounds: (methacryloxymethyl)methyldimethoxysilane; (methacryloxymethyl)methyldiethoxysilane; (methacryloxymethyl)dimethylmethoxysilane; diethylphosphatoethylmethyldiethoxysilane; 3-aminopropyltriethoxysilane; methacryloxypropyltrii sopropoxysilane; m-aminophenyltrimethoxysilane; 3-(acryloxypropyl)tris(trimethylsiloxy)silane; methacryloxypropyltriethoxysilane; N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; 2-(acryloxyethoxy)trimethylsilane; 3-methacryloxypropyltrimethoxysilane; acetoxypropyltrimethoxysilane; p-aminophenyltrimethoxysilane; 3-(acryloxypropyl)trimethoxysilane; diethylphosphatoethyltriethoxysilane; 3-(acryloxypropyl)trichlorosilane; 3-mercaptopropyltriethoxysilane; 3-(acryloxypropyl)methyldichlorosilane; 3-aminopropylmethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane; carboxyethylsilanetriol in sodium salt form; 3-mercaptopropylmethyldimethoxysilane; 4-aminobutyltriethoxysilane; methacryloxyethoxytrimethylsilane and; mixtures thereof.

5. The method according to claim 1, wherein at least one of the coating compounds and the sol-gel precursors include OH groups prior to step c).

6. The method according to claim 1, wherein the sol-gel precursors applied during step a) are in at least partially hydrolyzed form.

7. The method according to claim 1, wherein second heat treatment is performed after applying the second composition on the anchor layer.

8. The method according to claim 1, wherein the metal substrate includes aluminum.

9. The method according to claim 1, wherein the coating that is obtained constitutes a layer of paint or wherein the coating is obtained by a sol-gel method.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a succession of prior art steps for treating the surface of a metal substrate;

(2) FIG. 2 is a block diagram showing the succession of steps in an implementation of the method of the invention;

(3) FIGS. 3A to 3D are highly diagrammatic and fragmentary views showing the changes that occur when performing the various steps of a method of the invention; and

(4) FIG. 4 shows the bonding of sol-gel precursors of the anchor layer to the underlying metal substrate.

DETAILED DESCRIPTION OF IMPLEMENTATIONS

(5) FIG. 2 is a block diagram showing a succession of steps that can be performed in the context of the present invention. The steps in dashed-line boxes are optional.

(6) Initially, a first liquid composition is applied to the surface of a substrate, e.g. comprising aluminum (step 10). By way of example, the treated substrate may comprise an aluminum alloy, e.g. an alloy of aluminum and copper (2000 series aluminum alloy) or an alloy of aluminum and zinc (7000 series aluminum alloy). In a variant, the substrate comprises a steel.

(7) In an implementation, the treated substrate may be an anodized aluminum alloy, e.g. for use in a braking application in the field of aviation. The substrate may thus be for making a wheel or for making means to apply pressing force, such as a hydraulic ring. More generally, the treated substrate may be for constituting a casing or a primary part of an airframe.

(8) As mentioned above, the first composition includes sol-gel precursors of alcoxysilane type and/or sol-gel precursors of metallo-organic type. The first composition may advantageously include a single sol-gel precursor of alcoxysilane or metallo-organic type that is designed not to be completely condensed following step b).

(9) When the first composition includes sol-gel precursors of alcoxysilane type, the solvent may for example be an alcohol. In particular, when APTES is used, the solvent may include ethanol, and when MAPTMS is used, the solvent may include iso-propanol.

(10) More generally, the sol-gel precursors of alcoxysilane type may be dissolved in a light solvent such as ethanol, iso-propanol, n-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, acetic acid, propionic acid, butanoic acid, ethyl acetate, propyl acetate, and mixtures thereof. Sol-gel precursors of alcoxysilane type may be dissolved in a polar solvent other than water presenting high vapor pressure, greater than or equal to 4 millibars at 20 C., e.g. lying in the range 4 millibars to 30 millibars at 20 C. As explained above, when they are applied to the surface of the metal substrate, the sol-gel precursors of alcoxysilane type may be in a form that is at least partially hydrolyzed, e.g. as a result of adding acid water.

(11) The sol-gel precursors of alcoxysilane type may be present in the first composition at a concentration by weight greater than or equal to 4 grams per liter (g/L), e.g. greater than or equal to 20 g/L. By way of example, the sol-gel precursors of alcoxysilane type may be present in the first composition at a concentration by weight lying in the range 4 g/L to 40 g/L, for example.

(12) The sol-gel precursors of metallo-organic type may be dissolved in a light solvent such as ethanol, iso-propanol, n-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, acetic acid, propionic acid, butanoic acid, ethyl acetate, propyl acetate, and mixtures thereof. In general manner, the sol-gel precursors of metallo-organic type may be dissolved in a polar solvent other than water presenting a vapor pressure that is high, being greater than or equal to 4 millibars at 20 C., e.g. lying in the range 4 millibars to 30 millibars at 20 C.

(13) The sol-gel precursors of metallo-organic type may be present in the first composition at a concentration by weight greater than or equal to 3 g/L, e.g. greater than or equal to 14 g/L. By way of example, the sol-gel precursors of metallo-organic type may be present in the first composition at a concentration by weight lying in the range 3 g/L to 30 g/L, for example.

(14) During step a), the first composition may be applied using any known means, e.g. spraying, dipping the metal substrate in a bath including the first composition, or by means of an applicator such as a rag, or a brush. In an implementation, the surface of the metal substrate is not subjected to any pickling step prior to applying the first composition. Independently of the nature of the sol-gel precursors used, it is possible during step a) to apply a weight of sol-gel precursors per unit area of the metal substrate lying in the range 0.4 grams per square meter (g/m.sup.2) to 4 g/m.sup.2, e.g. in the range 0.4 g/m.sup.2 to 2 g/m.sup.2.

(15) Once the first composition has been deposited on the metal substrate, a first heat treatment is performed so as to form an anchor layer on the metal substrate (step 20). During the first heat treatment, a first temperature is used that is sufficient to eliminate all or part of the liquid medium from the first composition and to enhance bonding of the sol-gel precursors to the metal substrate. The first temperature and the duration for which it is applied are selected so as to avoid complete condensation of the sol-gel precursors among one another.

(16) Independently of the nature of the sol-gel precursors used, the first temperature used during step b) may, by way of example, be greater than or equal to 80 C., e.g. greater than or equal to 100 C. The first temperature used during step b) may, by way of example, be less than or equal to 180 C. The first temperature used during step b) may, by way of example, lie in the range 80 C. to 180 C., e.g. in the range 100 C. to 180 C.

(17) The duration for which the first temperature is applied during step b) may be less than or equal to 30 minutes (min). More precisely, for sol-gel precursors of alcoxysilane type, the duration for which the first temperature is applied during step b) may, by way of example, lie in the range 2 min to 10 min. For sol-gel precursors of metallo-organic type, the duration for which the first temperature is applied during step b) may, by way of example, lie in the range 10 min to 30 min.

(18) After step b) and before step c), it is possible to cool the anchor layer that forms, e.g. returning it to ambient temperature (20 C.)

(19) After performing step 20, a second composition is applied on the anchor layer (step 30). The second composition includes coating compounds suitable for obtaining a coating on the anchor layer by bonding together the sol-gel precursors and the coating compounds, as explained above, i.e. forming bonds between them. In an implementation, the coating compounds may be sol-gel precursors, the coating being to be obtained by a sol-gel technique.

(20) The coating compounds may be present in the second composition at a concentration greater than or equal to 0.1 moles per liter (mol/L), e.g. lying in the range 0.1 mol/L to 1 mol/L.

(21) Once the coating compounds have been applied, it is possible, by way of example, to perform second heat treatment at a temperature that is high enough to encourage the formation of bonds between the sol-gel precursors and the coating compounds (step 40). By way of example, the second temperature used during the second heat treatment may be greater than or equal to 80 C., e.g. greater than or equal to 100 C. By way of example, the second temperature may lie in the range 80 C. to 180, e.g. in the range 100 C. to 180 C. The second temperature may be used for a duration of at least 15 min, e.g. at least one hour.

(22) As an alternative, or in combination, the second heat treatment may serve to condense the sol-gel precursors among one another and/or to condense the coating compounds among one another, as explained above.

(23) Once step 30, and optionally step 40, have/has been performed, a coating is obtained on the anchor layer by bonds being formed between the sol-gel precursors and the coating compounds (step 50).

(24) Step c) may be performed directly after step b) (i.e. without any other treatment being performed between steps b) and c)).

(25) The coating obtained after step c) may constitute a layer of paint. The coating obtained after step c) may be obtained by a sol-gel technique when the coating compounds are sol-gel precursors.

(26) There follows a description of FIGS. 3A to 3D, which show the changes that occur when performing the various steps of the method. In these figures, the dimensions of the various layers are not to scale, for reasons of clarity.

(27) FIG. 3A shows the result obtained after performing step a) of the invention. As shown, a first composition 100 in the form of a solution having the sol-gel precursors 101 present therein is applied onto the metal substrate S. The sol-gel precursors 101 are present in a solvent 102 that may be as described above. After step b), the solvent 102 has been eliminated by evaporation so as to form an anchor layer 1 in contact with the metal substrate. The sol-gel precursors 101 present in the anchor layer 1 have developed bonds 105 with the metal substrate S (see FIG. 3B). As shown in FIG. 3B, the sol-gel precursors 101 present in the anchor layer after performing step b) are not condensed among one another (no bonding between the sol-gel precursors 101). It would not go beyond the ambit of the present invention if there were to be partial condensation among the sol-gel precursors 101 after step b), providing the precursors 101 retain OH groups and/or O-Alk groups suitable for interacting with the coating compounds so as to form bonds therewith.

(28) FIG. 4 shows the sol-gel precursors 101 fixing to the metal substrate S. In the example shown in FIG. 4, the metal substrate S is an aluminum substrate of surface that has been pickled (the substrate does not present a layer of oxidation at its surface), and the sol-gel precursors 101 that are applied to the surface of the substrate S are MAPTMS. As shown, the sol-gel precursors 101 form a bond 105 with the substrate S. This bond 105 is provided by a ligand group 104, in this example of methacryloxy type, which group forms a portion of the ligand organic function of the sol-gel precursors 101. The ligand group 104 constitutes a hydrophobic portion that tends to arrange itself beside the surface of the substrate S which also constitutes a hydrophobic region.

(29) Furthermore, the MAPTMS sol-gel precursors 101 in the example shown have been applied to the substrate S in partially hydrolyzed form. It is advantageous to apply the sol-gel precursors 101 in a form that is at least partially hydrolyzed so that they present hydrophilic portions that tend to point away from the surface of the substrate S. Thus, the residual OH and OCH, groups 103 tend in the majority to point away from the substrate S, thereby serving to improve interactions with the coating compounds that are applied subsequently, and consequently improving the adhesion of the coating to the anchor layer.

(30) Naturally, in a variant, the MAPTMS precursors could be applied in totally hydrolyzed form. During step b) there could still be partial condensation among the sol-gel precursors within the anchor layer.

(31) Thereafter, a second composition is applied on the anchor layer 1. This second composition includes coating compounds 201. In the example shown, the coating compounds 201 and the sol-gel precursors 101 have sufficient OH groups to ensure that bonds 205 form at ambient temperature between the sol-gel precursors 101 and the coating compounds 201 in order to ensure that the coating 2 adheres to the anchor layer 1 (see FIG. 3C).

(32) In an implementation, the thickness e of the coating 2 that is formed during step c) may be greater than or equal to 500 nanometers (nm), and is preferably greater than or equal to 1 micrometer (m). The thickness e corresponds to the greatest dimension of the coating 2 measured perpendicularly to the surface of the substrate S.

(33) It is then possible to perform second heat treatment so as to condense the sol-gel precursors 101 among each other and condense the coating compounds 201 among each other. Bonds 110 are thus created between the sol-gel precursors 101, and bonds 210 are created between the coating compounds 201 (see FIG. 3D). Such treatment serves advantageously to increase the hardness of the coating 2 and possibly of the anchor layer 1.

EXAMPLES

Example 1

Applying a First Composition Including Sol-Gel Precursors of Alcoxysilane Type

(34) In this example, two types of substrate were coated in accordance with the invention, namely: a polished substrate of 304 type stainless steel, and a mirror-polished substrate of aluminum.

(35) Prior to applying the first composition, the surface of the metal substrate was initially cleaned. By way of example, the cleaning may be performed by degreasing with acetone, rinsing in ethanol, and then in water, followed by drying in compressed air, or using a degreasing solution sold by the supplier Ceetal under the name Major Font NM at 5% in water in an ultrasound vessel. It is also possible to perform washing with deionized water, followed by drying using an air jet.

(36) Thereafter, the metal substrate was coated in a first composition including MAPTMS (3-methacryloxypropyltrimethylsilane) sol-gel precursors in solution in iso-propanol. The concentration of MAPTMS sol-gel precursors in the first composition laid in the range 2.48 g/L to 12.4 g/L. The first composition was sprayed on the metal substrate.

(37) After applying the first composition on the metal substrate, the solvent was evaporated by placing the substrate coated in the first composition in a stove that was maintained at a temperature of 100 C. for a duration lying in the range 2 min to 10 min. Thereafter, the substrate was extracted from the stove and returned to ambient temperature.

(38) An epoxy type coating was then formed on the resulting anchor layer.

(39) After the coating had been formed, the coated substrate was put into an oven that was maintained at a temperature of 150 C. for a duration of one hour in order to increase the hardness of the anchor layer and of the coating layer (condensation of condensable species present in these layers).

(40) Table 1 below summarizes the results obtained.

(41) TABLE-US-00001 TABLE 1 Results obtained by applying MAPTMS Scotch Pencil Coating Cross-cut Sclerometer Samples test hardness thickness test hardness Polished Not Not 10.7 m Class 1 Not 304 type torn scratched (ISO2409) scratched stainless off by H by 5N steel Mirror Not Not 12.3 m Class 1 Not polished torn scratched (ISO2409) scratched aluminum off by 2H by 4N

(42) The Scotch test serves to determine the adhesion of the coating to the underlying metal substrate. The pencil hardness test, the cross-cut test, and the sclerometer hardness serve to determine the hardness of the coating and of the anchor layer.

(43) The results given in Table 1 show that the method of the invention is particularly simple and makes it possible to obtain coatings that present excellent adhesion to a substrate and also very good hardness.

Example 2

Applying a First Composition Including Sol-Gel Precursors of Alcoxysilane Type

(44) In this example, the treated metal substrate was a 2000 series aluminum alloy.

(45) Prior to applying the first composition, the surface of the metal substrate may initially be cleaned as described in Example 1.

(46) Thereafter, the metal substrate was then coated in a first composition including APTES ((3-aminopropyl)-triehoxysilane) sol-gel precursors in solution in ethanol. The concentration of APTES sol-gel precursors in the first composition was 5 g/L. The solution was applied by spray gun and the thickness of the resulting film was about 2 m.

(47) After applying the first composition on the metal substrate, the solvent was evaporated by placing the substrate coated in the first composition in a stove maintained at a temperature of 120 C. for a duration lying in the range 2 min to 10 min. The substrate was then extracted from the stove and returned to ambient temperature. An epoxy type coating was then formed on the resulting anchor layer.

(48) After the coating had been formed, the coating substrate was put into a stove maintained at a temperature of 120 C. for a duration of one hour in order to increase the hardness of the anchor layer and of the coating (condensation of condensable species present in these layers).

(49) Table 2 below summarizes the results obtained.

(50) TABLE-US-00002 TABLE 2 Results obtained by applying APTES Scotch Pencil Coating Cross-cut Sclerometer Samples test hardness thickness test hardness MB aviation Not Not 4 m Class 1 Not aluminum torn scratched (ISO2409) scratched off by 5H by 4N

(51) The results given in Table 2 show that the method of the invention is particularly simple and makes it possible to obtain coatings that present excellent adhesion to a substrate and that also present very good hardness.

Example 3

Applying a First Composition Including Sol-Gel Precursors of Metallo-Organic Type

(52) In this example, two types of substrate were coated in accordance with the invention, namely: a polished 304 type stainless steel substrate and a mirror polished aluminum substrate.

(53) Prior to applying the first composition, the surface of the metal substrate may initially be cleaned as described in Example 1.

(54) Thereafter, the metal substrate was coated in a solution of iron acetate in propionic acid with the iron acetate being at a concentration of 0.05 mol/L.sup.1. The iron acetate forms iron propionate in the solution.

(55) After applying the first composition to the metal substrate, the solvent was evaporated by placing the substrate coated in the first composition in a stove maintained at a temperature of 150 C. for a duration lying in the range 10 min to 30 min. The substrate was then extracted from the stove and returned to ambient temperature. An epoxy type coating was then formed on the resulting anchor layer.

(56) After the coating was formed, the coated substrate was put into a stove maintained at a temperature of 150 C. for a duration of one hour in order to increase the hardness of the anchor layer and of the coating (condensation of the condensable species present in these layers).

(57) Table 3 below summarizes the results obtained:

(58) TABLE-US-00003 TABLE 3 Results obtained by applying a solution of iron acetate in propionic acid Scotch Pencil Coating Cross-cut Sclerometer Samples test hardness thickness test hardness Polished Not Not 3.2 m Class 0 Not 304 type torn scratched (ISO2409) scratched stainless off by 6H by 4H steel Mirror Not Not 4.3 m Class 1 Not polished torn scratched (ISO2409) scratched aluminum off by F by 5N

(59) The term including/containing a should be understood as including/containing at least one.

(60) The terms lying in the range . . . to . . . or from . . . to . . . should be understood as including the limits.