Abstract
A corrosion inhibiting additive and a corrosion inhibiting coating including the additive for providing corrosion resistance to a metal are provided. The corrosion inhibiting additive includes a first corrosion inhibiter comprising an organic cation in a cation exchange resin and a second corrosion inhibiter includes a phosphate compound. The corrosion inhibiting additive is for incorporation into a coating having at least a polymer binder.
Claims
1. A corrosion inhibiting additive comprising: a first corrosion inhibitor comprising an organic cation in a cation exchange resin; and a second corrosion inhibitor comprising a phosphate compound.
2. The corrosion inhibiting additive according to claim 1, wherein the phosphate compound comprises one or more metal phosphates.
3. The corrosion inhibiting additive according to claim 1, wherein the phosphate compound comprises a polyphosphate compound or a phosphosilicate compound.
4. The corrosion inhibiting additive according to claim 2, wherein the metal phosphate is zinc phosphate.
5. The corrosion inhibiting additive according to claim 1, wherein the first and second corrosion inhibitor are particulate.
6. The corrosion inhibiting additive according to claim 1, wherein the first and second corrosion inhibitors are provided as a mixture, and the mixture comprises a range of usable weight ratios of first corrosion inhibitor to second corrosion inhibitor of between 2:15 and 15:2 respectively, or between 1:5 and 5:1 respectively, or between 1:4 and 4:1 respectively, or between 1:3 and 3:1 respectively.
7. A coating for a metal substrate comprising: a first corrosion inhibitor comprising an organic cation in a cation exchange resin; and a second corrosion inhibitor comprising a phosphate compound; wherein the first and second corrosion inhibitors are provided in a polymer binder.
8. The coating according to claim 7, wherein weight ratios of the first corrosion inhibitor to the second corrosion inhibitor comprise between 2:15 and 15:2 respectively, or between 1:5 and 5:1 respectively, or between 1:4 and 4:1 respectively, or between 1:3 and 3:1 respectively.
9. The coating according to claim 7, wherein the combined first and second corrosion inhibitor comprise between 4 and 30 weight percent of a coating weight in wet form.
10. The coating according to claim 9, wherein the combined first and second corrosion inhibitor comprises between 5 and 20 weight percent of the coating weight in wet form.
11. The coating according to claim 7, wherein the polymer is liquid at room temperature and pressure.
12. The coating according to claim 7, wherein the polymer binder is selected from one or more of an acrylic, polyester, epoxy, silicone, alkyd polyurethane or polyvinyl butyral.
13. The coating according to claim 7, wherein the organic cation is an azole or oxime.
14. The coating according to claim 7, wherein the organic cation is benzotriazole or a derivative thereof.
15. The coating according to claim 7, wherein the cation exchange resin is an organic cation exchange resin.
16. The coating according to claim 15, wherein the organic cation exchange resin is styrene and/or divinylbenzene copolymer with a negatively charged group.
17. (canceled)
18. A method of protecting a metal substrate comprising: applying a corrosion inhibiting coating to the substrate, the corrosion inhibiting coating comprising: a first corrosion inhibitor comprising an organic cation in a cation exchange resin; a second corrosion inhibitor comprising a phosphate compound; and a polymer binder.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] An embodiment of the invention will now be described by way of example only with reference to and as illustrated in the following figures and examples in which;
[0039] FIG. 1 shows: a schematic exploded view of a typical metal substrate and coating layers;
[0040] FIG. 2 shows: the action of a corrosion inhibitor in the event of a breach of coating layers to reach the metal substrate;
[0041] FIG. 3a-d are schematic representations of the stages of protection of a substrate with FIG. 3e showing a magnified view;
[0042] FIG. 4 are images of corrosion after 1000 hours under ASTM B117 salt spray on steel panels comparing the corrosive effect of the coatings with a polymer binder carrying zinc phosphate with the same coatings but including a corrosion inhibitor comprising an organic cation in a cation exchange resin;
[0043] FIGS. 5a and 5b are images showing a comparison of corrosion for identical steel panels under test conditions of 250 hours under ASTM B117 salt spray where the panel in FIG. 4a is coated with a commercially available manufactured single layer direct to metal (DTM) primer including a first corrosion inhibitor and the panel in FIG. 4b is coated with a commercially available single layer DTM primer containing only zinc phosphate;
[0044] FIGS. 6a and b are schematic representations of a standard corrosion test known as a Scanning Kelvin Probe (SKP) delamination test;
[0045] FIGS. 7a and b are images showing the effect of delamination upon a non-commercial test coating comprising polyvinyl butyral in ethanol (of 15.5 weight %) containing zinc phosphate in FIG. 6a and containing a first corrosion inhibitor in FIG. 6b using the testing apparatus as shown in FIG. 5;
[0046] FIGS. 8a and b are images of corrosion of mild steel test pieces coated with a polyvinyl butyral in ethanol coating containing both a first corrosion inhibitor and zinc phosphate in different weight percentages;
[0047] FIGS. 9a and b are images of corrosion of hot dip galvanised steel using the same coatings and weight percentages as used in the test results presented in FIGS. 7a and b;
[0048] FIG. 10 is a visual comparison between 2024 T3 aerospace aluminium comparing a coating according to the present invention (a) versus two known commercially available chromated coatings (b) and (c);
[0049] FIG. 11 is a visual comparison of the same coatings on cold rolled steel as presented in FIG. 10.
DETAILED DESCRIPTION OF AN EMBODIMENT OF THE INVENTION
[0050] The present invention has been developed to provide an alternative corrosion inhibitor.
[0051] Referring to FIG. 3, there is a metal substrate 2 on top of which is a primer 8 with first and second corrosion inhibitors 30, 32 dispersed therethrough. The primer is then coated with a barrier coating 10. The first corrosion inhibitor 30 comprises an organic cation in a cation exchange resin, provided in particulate form. As an example only, the organic cation is benzotriazole or a derivative thereof, and the cation exchange resin is styrene and/or divinylbenzene copolymer with a negatively charged sulphonated functional group. The second corrosion inhibitor 32 comprises a phosphate compound such as zinc phosphate, strontium polyphosphate, or calcium strontium phosphosilicate as examples only also provided in particulate form. The first and second corrosion inhibitors are combined with a polymer binder in desired quantities for the application thereby providing a coating for a metal, and applied to the metal substrate 2 in liquid form and allowed to dry before application of the barrier coating 10.
[0052] It will be appreciated that the first and second corrosion inhibitors 30,32 may either be combined then added to a polymer binder or added independently. Either way, the particulate corrosion inhibitors are dispersed through the coating.
[0053] The coating comprises between 2 and 15 weight percent of the first corrosion inhibitor of the coating in wet form, and between 2 and 15 weight percent of the second corrosion inhibitor of the coating in wet form. Even more preferably, the coating may comprise between 2 and 10 weight percent of the first corrosion inhibitor of the coating in wet form, and between 2 and 10 weight percent of the second corrosion inhibitor of the coating in wet form. It has been determined that there is a beneficial corrosion resistance effect across such a range of weight percentages, and a reduction in the relative weight percent of the second corrosion inhibitor can be achieved as the first corrosion inhibitor reduces the rate of leaching out of the second corrosion inhibitor. The first and second corrosion inhibitor also preferably comprises a range of usable ratios of first corrosion inhibitor to second corrosion inhibitor of 1:5 and 5:1 respectively.
[0054] The steps of protection of a metal substrate 2 will now be described under conditions of a corrosive environment due to breach of the protective coatings of the substrate. Referring to FIG. 3b, the barrier coating 10 and the primer 8 have been breached. Corrosive ions 34 are therefore capable of communicating with the substrate 2 thereby effecting corrosion. Referring to FIG. 3c, when the electrolyte comprising corrosive ions 34 is present (comprising cations and anions) the first corrosion inhibitor 30 acts by cations being sequestered by the cation exchange resin which releases protonated benzotriazole into the electrolyte where it is deprotonated (this will moderate the under film pH) and will eventually turn into its anionic form at pH's above 7.2. Another beneficial effect is when the benzotriazole is in a neutral form a barrier layer can form on the metallic surface. The azole group at one end forms a bond with the metallic surface and also metallic ions released resulting from the anodic dissolution. The adsorbed benzotriazole is thought to stifle electron transfer reactions while the precipitate 36 formed by reaction of benzotriazole anions with metal cations forms an inhibitive film which blocks the surface to further corrosive attack. This response is very fast, minimising the corrosion progression.
[0055] In addition to the response of the first corrosion inhibitor 30, under these conditions of aqueous environment, phosphate anions dissolve out of the phosphate salt, which then react with remaining metal cations to form a precipitate of metal phosphate 40. The combined precipitate formed from the first and second corrosion inhibitors provides a strong protective layer to prevent further corrosion. Accordingly, as shown in more detail in FIG. 3e, there is quick exchange of corrosion ions into the ion exchange resin, releasing in a preferred embodiment benzotriazolate (BTA) rapidly to form a film over the metal surface and complexing with any dissolved metal ions 42. The phosphate then has enough time to dissolve into the electrolyte. Effective protection is therefore not dependent on enough concentration of phosphate anions appearing quickly to form a protective layer, rather the phosphate anions a slower to appear but when they do react with the metal cations to ensure formation of a continuous film and fill in between any gaps in the BTA. Layers and layers are built up of the combination of the two precipitates.
[0056] The coating as described may be used in a multi-layer system on coated Hot Dip Galvanised (HDG) Steel, to protect from under-film corrosion. It may also be used on steel without galvanisation to protect from corrosion.
[0057] In each of the following examples, the first corrosion inhibitor comprises benzotriazole cation in a divinylbenzene copolymer with a negatively charged sulphonated functional group cation exchange resin.
[0058] FIGS. 4a and 4b are comparative photographs of the same steel panels following 1000 hours in a corrosive environment comparing in FIG. 4a the steel panel coated with a commercially available two pack epoxy primer having a composition including 3 weight percent zinc phosphate. It will be appreciated that for each panel a cross has been scored through the coating and into the panel in accordance with standard corrosion testing procedure. This is compared to FIG. 4b which shows the same steel substrate coated with the same two pack epoxy primer with the addition of 5 weight percent of a first corrosion inhibitor in particulate form comprising an organic cation in a cation exchange resin (benzotriazole cation in a divinylbenzene copolymer with a negatively charged sulphonated functional group cation exchange resin. The significant reduction in corrosion presented in FIG. 4b is readily apparent.
[0059] FIG. 4c is an alternative industrially available two pack epoxy primer having 3 weight percent zinc phosphate therein where FIG. 4c shows the extent of corrosion following 1000 hours. In comparison, FIGS. 34 and 4e show the incorporation in the same two pack epoxy primer of 5 percent and 1 percent of a first corrosion inhibitor comprising an organic cation in a cation exchange resin respectively. It is apparent that the inclusion of the first corrosion inhibitor has a significant effect upon the reduction in visible corrosion.
[0060] FIGS. 4f and 4g show the same steel panel with a comparison of utilisation of a two pack epoxy and top coat including 3 weight percent of zinc phosphate in FIG. 4f and in FIG. 4g showing the same two pack epoxy and top coat including the same weight percentage of zinc phosphate together with an additional 5 weight percent of a first corrosion inhibitor comprising an organic cation in a cation exchange resin. The reduction in corrosion with the combination of zinc phosphate and the first corrosion inhibitor as presented in FIG. 4g is readily apparent.
[0061] FIGS. 5a and 5b show identical steel panels (where the panel in FIG. 5a is coated with a commercially available single layer direct to metal (DTM) primer including 5% loading of the first corrosion inhibitor. The panel in FIG. 4b is coated with a commercially available single layer DTM primer containing only zinc phosphate of 25%. For each panel the primer was not coated with a topcoat. Following testing under standard ASTM B117 salt spray testing conditions the bond between the coating and metal has been significantly weakened leading to delamination. In each test gentle mechanical action on the coating led to differing extent of delamination. It is readily apparent that the panel containing only zinc phosphate as presented in FIG. 5b underwent significant delamination of the primer from the panel due to corrosion of the panel affecting the ability of the coating to adhere to the panel. Conversely however, the panel as presented in FIG. 5a where the primer contains the first corrosion inhibitor only there is some delamination however requires mechanical force to remove the coating showing an improvement of the first corrosion inhibitor over a primer containing zinc phosphate. Importantly this effect is apparent in a commercially available DTM primer.
[0062] FIGS. 6a and b are schematic representations of a standard corrosion test known as a Scanning Kelvin Probe (SKP) delamination test. In this test, a metal substrate 2 is provided and a test area 4 is defined between an adhesive tape 6 and insulating tape guide 8. A protective coating 10 for testing is spread across the test area 4 using a coating bar 12 thereby covering the test area as shown in FIG. 6b. An adhesive tape/coating barrier 14 is provided to define an electrolyte well 16 and a corrosion site 18 is therefore provided at the interface of the electrolyte and the test area 4. A scanning kelvin tip probe 20 can be used to monitor corrosion in real time. The action of the electrolyte on the interface between the coating and underlying metal causes cathodic disbondment failure which results in the destruction of the bond between the underlying metal and the coating. As the corrosion establishes and progresses, the cathodic disbondment front moves along the test piece.
[0063] Referring to FIGS. 7a and b, the effect of delamination upon a test coating comprising polyvinyl butyral in ethanol (of 15.5 weight %) containing zinc phosphate in FIG. 7a and containing the first corrosion inhibitor in FIG. 7b is presented using the testing apparatus as shown in FIG. 6. The location of the electrolyte well 16 is shown. The coating as presented in FIG. 7b does not contain any zinc phosphate. The effect of delamination can clearly be viewed where both test pieces underwent complete delamination. This compares to the test results of FIG. 5 where delamination was decreased (but not prevented) in a commercially available coating rather than a simple test coating.
[0064] A direct comparison of the results presented in FIG. 7 can be made with the results presented in FIG. 8, where mild steel test pieces were coated with a test coating comprising polyvinyl butyral in ethanol containing both the first corrosion inhibitor and zinc phosphate. The coating in FIG. 8a contains 8 weight percent first corrosion inhibitor and 5 weight percent zinc phosphate, and the coating of FIG. 8b contains 4 weight percent first corrosion inhibitor and 2.5 weight percent zinc phosphate. It is clear that the delamination effect is minimal. Thus, the synergistic effect of the first corrosion inhibitor and the metal phosphate on the reduction in corrosion is apparent.
[0065] Referring to FIGS. 9a and b, presented are test results for hot dip galvanised steel using the same coatings and weight percentages as used in the test results presented in FIGS. 8a and b. Direct comparison is made to the same substrate in FIG. 9c which was coated with a coating without the first corrosion inhibitor, clearly showing complete delamination has occurred. FIGS. 9a and b show minor delamination effects. Again, the significant synergistic effect of utilising both first and second corrosion inhibitors as disclosed herein.
[0066] FIG. 10 is a comparison between 2024 T3 aerospace aluminium comparing a coating according to the present invention (a) versus two known commercially available chromated coatings (b) and (c). The coating tested in FIG. 10a is a coating according to the present invention comprising 5 PVC first corrosion inhibitor and 20 PVC second corrosion inhibitor in a polymer binder and shows delamination after testing according to a Scanning Kelvin Probe (SKP) delamination test. It is clear that the present invention strongly outperforms traditional chromate-based coatings.
[0067] FIG. 11 is a visual comparison of the same coatings and order of presentation on cold rolled steel as presented in FIG. 10. Again, the effectiveness of an illustrative embodiment of the present invention is clearly visually presented.
[0068] The present invention has been described by way of example only and it will be appreciated by the skilled addressee that modifications and variations may be made without departing from the scope of protection disclosed herein.
