Utilization of moo3 as corrosion inhibitor and coating compositions containing such inhibitor

FIELD: corrosion protection.

SUBSTANCE: invention relates to anticorrosion compositions for metallic parts, in particular to utilization of MoO3 as agent enhancing anticorrosive properties of composition for anticorrosion coating based on dispersed metal, containing zinc of zinc alloy in aqueous phase (30-60% water in dispersion) and containing binding agent. Compositions for anticorrosion coating of metallic parts are disclosed containing such corrosion inhibitor (MoO3); at least one dispersed metal selected from group composed of zinc, aluminum, chromium, manganese, nickel, titanium, and alloys thereof; organic solvent; thickening agent; silane-based binder; optionally sodium, potassium, or lithium silicate; and water in amount from 30 to 60% by weight. Disclosed are also anticorrosion coating and metallic substrate with deposited anticorrosion coating prepared from above-defined composition.

EFFECT: improved resistance of composition to salt fog action.

22 cl, 2 dwg, 6 tbl, 3 ex

 

The purpose of this invention to provide an anticorrosive coatings for metal parts, which preferably does not contain compounds hexavalent chromium and has superior anti-corrosion properties.

This invention is used for the metal parts of any type, in particular for steel and cast iron parts, which should have good anti-corrosive characteristics, as they are used, for example, in the automotive industry. The geometric shape of parts to be processed, it does not matter if anticorrosive compositions can apply reliable methods that could be used in industry.

Another objective of this invention is, in particular, to improve anti-corrosion properties of parts that are processed compositions for coatings that do not contain compounds of hexavalent chromium.

To date, proposed many solutions for anticorrosion treatment, which contain compounds of hexavalent chromium. Although these solutions are usually satisfactorily protects against corrosion treated their metal parts, however, they are subjected to increasingly severe criticism because of the consequences of their application, which creates the danger of poisoning, and specifically in the region of the consequences of using these solutions for the environment.

As a result of such criticism appeared recommendations of the various compositions for anti-corrosive treatment, not containing compounds hexavalent chromium. Some of these songs include dispersed metal, such as zinc or aluminum. However, when such compositions are in the form of aqueous dispersions, their stability is limited. This prevents long-term protection and long-term storage.

In the context of this invention by the applicant, it was found that anti-corrosion properties and stability of various anti-corrosion compositions for coating can be improved by the introduction of a molybdenum oxide (MoO3) as a corrosion inhibitor.

Still no reports of the use of molybdenum oxide (MoO3) as a corrosion inhibitor in systems containing water phase. Some molybdates, such as ions MoO42-, have already been described as corrosion inhibitors. However, the applicant could show that the addition of molybdate, such as zinc molybdate, a number of conventional anticorrosive compositions absolutely does not improve their properties.

This invention relates more specifically to the use of molybdenum oxide MoO3as an agent to enhance the corrosion characteristics of the composition for coatings made on the basis of the fine metal is, containing zinc or zinc alloy in an aqueous phase. The results were even extended to the composition for coatings containing compounds of chromium (VI). It is another purpose of this invention.

Not limited to this explanation, it is still possible to believe that in the specific case of an anticorrosive composition for coating on the basis of dispersed metal the presence of molybdenum oxide MoO3allows you to improve the regulation of corrosion protection implemented dispersed metal powder in suspension in the composition.

In accordance with their specific feature, dispersed metals have a lamellar (scaly) shape in which the thickness of the flakes is from 0.05 to 1 μm, as measured using laser diffraction equivalent diameter (D50) is from 5 to 25 microns; more specifically, the subject invention is the use of molybdenum oxide MoO3in compositions containing zinc in the aqueous phase.

In accordance with another feature of the present invention, the molybdenum oxide MoO3applied in the form of essentially pure orthorhombic crystalline form, the content of molybdenum in which greater than about 60 wt.%.

Certain advantages are obtained when the molybdenum oxide MoO3used in anti-corrosion compositions in the form of particles having the size of the market from 1 to 200 microns.

More specifically, the object of the present invention are compositions for corrosion-resistant coating of metal parts, which include:

at least one of dispersed metal;

- organic solvent;

- thickener;

- binder-based silane, preferably containing epoxy functional groups;

- molybdenum oxide (MoO3);

perhaps, sodium silicate, potassium or lithium;

is water.

The relative ratios of different components in such compositions can vary within wide limits. However, it was found that the content of molybdenum oxide MoO3is preferably from 0.5 to 7 wt.% and even more preferably in the range of 2 wt.% of the total weight of the composition.

Dispersed metal present in the composition, may be selected from zinc, aluminum, chromium, manganese, Nickel, titanium, their alloys, intermetallic compounds and mixtures thereof. Here, you specify that if the recommended composition for coating preferably does not contain CrVInevertheless, it may contain some amount of metallic chromium. In practice it has appeared that it is very desirable the presence of zinc.

Advantageously, if the content of the dispersed metal is from 10 to 40 wt.% by weight of the entire composition.

Anticorrosive composition for coating according to this innovation is the invention preferably contains zinc and/or aluminum and preferably includes zinc.

As indicated above, the composition of this type has mainly aquatic nature and, therefore, preferably contains from 30 to 60 wt.% water. However, the composition may be enriched with an organic solvent, preferably a solvent, soluble in water, which allows to improve the corrosion performance of the composition. For this purpose, the composition contains from 1 to 30 wt.% organic solvent by weight of the total composition. However, it is important that the content of the organic solvent is not more than approximately 30%.

In a favorable embodiment of the present invention in the composition using an organic solvent, for example, consisting of glycol ether, specifically diethylene glycol, triethylene glycol and dipropyleneglycol.

According to another feature of the present invention coating composition also contains 0.005 to 2 wt.% thickener, specifically a derivative of cellulose, more specifically hydroxymethylcellulose, hydroxyethyl cellulose, hydroxypropylcellulose, hypromellose, xanthan gum or related thickener polyurethane or acrylic type.

The composition of this invention may also contain mineral rheological agents of type lyophilic silica or clays.

In such compositions also use the binder is, preferably the organic silane containing organic functional groups, used in quantities of from 3 to 20 wt.%. Organic functional groups can be represented by vinyl, methacrylate and amino groups, but preferred are epoxy groups to improve the characteristics of the coating and increase the stability of the composition. The advantage is the ability of the silane easily dispergirujutsja in the aquatic environment, and it is preferably able to be dissolved in such an environment. Preferably the most useful silane is a silane with epoxy functional groups, for example β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 4(trimethoxysilyl)-1,2-epoxybutane or γ-glycidoxypropyltrimethoxysilane.

Finally, the composition for anti-corrosion coating according to this invention may also contain, in addition to the above organic solvent, white spirit (the maximum amount is up to about 10 wt.%), to improve the ability of anti-corrosion compositions be applied to metal parts by spraying, dipping or immersion with the rotation.

Have an advantage, when the composition may also contain sodium silicate, potassium or lithium, preferably in quantities of from 0.05 to 0.5 wt.%.

Naturally, this invention is that the same applies to the anti-corrosion coatings which are applied to metal parts using above-mentioned compositions, and put them by spraying, dipping or dipping with rotation, followed by curing at a temperature of between 70 and 350°C for approximately 30 minutes

According to an advantageous variant implementation of the invention, the corrosion-resistant coating obtained from the coating process, including before surgery curing drying metal parts coated, preferably at a temperature of about 70°C for approximately 20 minutes under these conditions, the thickness of the coatings thus, ranges from 3 μm to 15 μm, preferably from 5 to 10 microns.

In the examples presented later in this application for comparison were subjected to test various types of corrosion inhibitors in the scope of this study, which was conducted with the aim to improve the corrosion properties of various compositions and specifically reference composition called GEOMET®that is described in U.S. patent No. 5868819 included in this application by reference.

Here are the basic corrosion inhibitors, which are produced by the industry and are commercially available. They are listed below by chemical categories, in each case specifying the origin of the product and its name is part.

EXAMPLE 1

Reference composition GEOMET®corresponds to the following formula:

Deionized water38,60%
Dipropyleneglycol (DPG)10,29%
Boric acid0,65%
SYMPERONIC®NP41,51%
SYMPERONIC®NP91,64%
SILQUEST®A1878,66%
Zinc*32,12%
Aluminum**5,08%
SCHWEGO FOAM®0,4%
NIPAR®S100,71%
AEROSOL®TR700,53%

* Zinc (particles which are in the form of flakes) in approximately 95% pasta in white-spirit: zinc 31129/93 from the company ECKART WERKE.

** Aluminum (particles which are in the form of flakes) in approximately 70% paste in dipropyleneglycol: CHROMAL VIII®from the company ECKART WERKE.

To conduct experiments to compare the above corrosion inhibitors, receive various baths (solutions for baths) by adding 1 g of the inhibitor to 9 ml of water, and the resulting dispersion retain for 1 h and then the mixture is dobavlaut to 90 g of the above-mentioned reference composition GEOMET ®and stirred for 3 hours

The first layer of this composition to be tested is applied through terminal No.38 (Conway). Drying is carried out at 70°C for approximately 20 min, and then carry out the curing at 300°C for approximately 30 minutes

The second coating layer is applied using the same procedure.

The plate thus treated, and then tested in salt spray. The results of resistance tests in salt spray tested for various coatings are presented in table 1, below.

TABLE 1
NatureThe exposure time (hour)
inhibitorThe name of the inhibitorsalt fog up
appearance red
rust
StandardGEOMET112
Modifica-

rowanne

phosphate

zinc
GEOMET + ZPA134
GEOMET + ZMP122
GEOMET + SAPP66
GEOMET + SRPP66
GEOMET + ZCP66
GEOMET + ZCPP88
GEOMET + CAPP66
GEOMET + ACTIROX 21366
GEOMET + HALOX 39166
GEOMET + K WHITE 8488
The molybdatesGEOMET + ACTIROX 10266
GEOMET + ACTIROX 10688
GEOMET + MW 21288
GEOMET + MW MZAP88
GEOMET + Na2MoO466
BoratesGEOMET + BUTROL44
GEOMET + BUSAN112
GEOMET + HALOX 223066
Different

inhibitors
GEOMET + SHIELDEX112
GEOMET + ALCOPHOR 82766
GEOMET + IRGACOR 193088
GEOMET + IRGACOR 140588
GEOMET + CGCI88
GEOMET + HALOX FLASH X66
GEOMET + IRGAMET 4244
GEOMET + IRGAMET BTAM66
InventionGEOMET + MoO3*518
* MoO3: POR from CLIMAX Company

In addition, more specific results on the stability of the coating to the effects of salt fog as is uncle duration of the bath and, therefore, its stability at 4°and 20°respectively, are given in the attached figures 1 and 2.

These two figures clearly shows that in each case, on the one hand, anticorrosion properties of the composition containing molybdenum oxide MoO3markedly improved and, on the other hand, anti-corrosion properties are better preserved over time, when molybdenum oxide is added to the composition.

EXAMPLE 2

Experiments two other types of conduct for comparison inhibitors: some composition GEOMET®and other composition DACROMET®based on hexavalent chromium.

The formulations of these compositions are given in tables 2, 3.

TABLE 2
GEOMET®
EductConcentration in%

songs without MoO3
Concentration in%

song MoO3
Deionized water38,6037,83
Dipropyleneglycol10,2910,08
Boric acid0,650,64
SYMPERONIC NP4®1,511,48
SYMPERONIC NP9®1,641,61
SILQUEST®A1878,66of 8.47
Zinc*32,1231,48
Aluminum**5,08to 4.98
SCHWEGO FOAM®0,40,21
NIPAR®S100,710,70
AEROSOL®TR700,530,52
MoO3***02
* Zinc (particles which are in the form of flakes) in approximately 95% pasta in white-spirit: zinc 31129/93 from the company ECKART WERKE.

** Aluminum (particles which are in the form of flakes) in approximately 70% paste in dipropyleneglycol: CHROMAL VIII®from the company ECKART WERKE.

*** MoO3: POR from CLIMAX Company
SYMPERONIC®:non-ionic surfactants
SILQUEST®A187:γ-glycidoxypropyltrimethoxysilane
SCHWEGO FOAM®:antifoam coal is hydrogen type
NIPAR®S10:the nitropropane
AEROSOL®TR70:anionic surface-active substance.

TABLE 3
DACROMET®
EductConcentration in%

songs without MoO3
Concentration in %

in song MoO3
Deionized water47,8644,90
Dipropyleneglycol15,9515,63
PGME acetate1,561,53
Chromic acid3,81to 3.73
REMCOPAL®3340,720,71
REMCOPAL®3390,720,71
Zinc*23,6123,14
Aluminum**3,063,00
Boric acid1,301,27
ZnO1,411,38
MoO3***02
* Zinc (particles which have fo the mu scales) in the form of approximately 95% pasta in white-spirit: zinc 31129/93 from the company ECKART WERKE.

** Aluminum (particles which are in the form of flakes) in approximately 70% paste in dipropyleneglycol: CHROMAL VIII®from the company ECKART WERKE.

*** MoO3: POR from CLIMAX Company

REMCOPAL®: non-ionic surfactants.

It should be noted that the oxide powder of molybdenum each time enter into a tub of GEOMET®or DACROMET®in the form of dust. Bath homogenized by stirring with a speed of 450 revolutions per minute using a dispersion blade.

Test anticorrosive compositions are applied to the plates (10 cm x 20 cm) from cold-drawn steel with low carbon content by a rod (Conway), followed by preliminary drying at 70°C for approximately 20 min and then curing in an oven at 300°C for 30 minutes

In the case of applying the composition for corrosion protection screws compositions are applied by dipping with the rotation and then utverjdayut under the same conditions used in the case of plates.

The observed results in resistance in salt spray to ISO 9227 schematically presented in table 4.

TABLE 4
ProductSubstrateCoating weight**Stand is here in salt

the fog*
Without MoO3C 2%MoO3
Water

GEOMET®
Plate32288> 840
Water

GEOMET®
Screws30144504
DACROMET®Screws24600744
* Time (in hours) of exposure in salt spray before the appearance of red rust.

** In grams per 1 square meter of coated surface, the coating thickness is from about 6 μm to about 8 μm.

Thus, it is obvious that the introduction of molybdenum oxide of Moo3in the composition in the aqueous phase GEOMET®or DACROMET®containing dispersed zinc, very significantly improves the durability of the above compositions to the effects of salt fog.

Another aspect of this invention consists in the addition of alkali metal silicate to the anticorrosive composition in amounts of from 0.05 to 0.5 wt.%.

Adding alkali metal silicate such as sodium silicate, greatly increases cohesion (adhesion) of the coating film properly.

This is specifically illustrated by the following example for comparison shown in table 5.

The USE of the 3

In this example, the cohesion estimate by applying a transparent adhesive paper on the surface and quickly removing it. Cohesion evaluate on a scale from 0 (complete removal of the coating film) to 5 (film coating completely removed).

TABLE 5
EductSong

contains silicate

(concentration

given in % )
The composition contains

silicate

(concentration

given in % )
Deionized water38,1337,96
Dipropyleneglycol10,0810,08
Boric acid0,640,64
Symperonic NP4®1,481,48
Symperonic NP9®1,611,61
The silane A®of 8.47of 8.47
Zinc 31129/9331,4831,48
Aluminum CHROMAL VIII®to 4.98to 4.98
Schwegofoam®0,210,21
NIPAR S10®0,70,7
AEROSOL TR70®,52 0,52
MoO311
Sodium silicate grade 4200,17
Xanthan gum (1)0,70,7

(1) a Thickener to adjust the viscosity of the composition during the coating process.

The composition is applied to the plates of steel, which previously degreased, using Conway rod to obtain a coating weight of 30 g/m2. Then the plates utverjdayut under the conditions described above.

These plates are then subjected to test for exposure to saline mist according to ISO 9227 and assess the cohesion of the coating film. The results of these tests are presented in table 6.

TABLE 6
Song

contains silicate

alkaline metal
The composition of

contains silicate

alkaline metal
The saline mist

(the number of hours

keeping up the appearance of

red rust)
694720
Cohesion1/55/5

The data of this table show that even if the resistance cohesion does not change significantly, cohesion, on the contrary, forces the but growing.

1. The use of Moo3as an agent to enhance the anticorrosion properties of the composition for anti-corrosion coatings on the basis of dispersed metal containing zinc or zinc alloy in the aqueous phase, and containing a binder and from 30 to 60 wt.% water.

2. The use according to claim 1 for improving the efficiency of corrosion protection implemented dispersed metal used preferably in the form of scales.

3. The use according to claim 1 or 2, characterized in that the composition for anti-corrosion coating contains a binder based silane, preferably containing functional epoxy group.

4. The use according to claims 1 to 3, characterized in that the molybdenum oxide of Moo3is an essentially pure orthorhombic crystalline form, the content of molybdenum in which more than 60 wt.%.

5. The use according to claims 1 to 4, characterized in that the molybdenum oxide of Moo3is in the form of particles having a size of from 1 to 200 microns.

6. The use according to claims 1 to 5, characterized in that the composition for anti-corrosion coating contains sodium silicate, potassium or lithium, preferably in quantities of from 0.05 to 0.5 wt.%.

7. Composition for corrosion-resistant coating of metal parts, characterized in that it includes at least one of dispersed metal; an organic solvent; a thickener; a binder on the Nove silane, preferably containing epoxy functional groups; molybdenum oxide (Moo3); it is possible that the silicate of sodium, potassium or lithium and water in an amount from 30 to 60 wt.%.

8. Composition for corrosion-resistant coating of metal parts according to claim 1, characterized in that it contains from 0.5 to 7 wt.% and preferably 2 wt.% molybdenum oxide (Moo3).

9. Composition for corrosion-resistant coating of metal parts according to claim 7, characterized in that it contains from 10 to 40 wt.% at least one of the dispersed metal.

10. Composition for corrosion-resistant coating of metal parts according to one of claims 7 to 9, characterized in that the dispersed metal selected from zinc, aluminum, chromium, manganese, Nickel, titanium and their alloys, intermetallic compounds and mixtures thereof.

11. Composition for corrosion-resistant coating of metal parts according to claims 7 to 10, characterized in that the dispersed metal selected from zinc (with particles in the form of flakes) and/or aluminum (with particles in the form of flakes) and preferably includes zinc particles in the form of flakes).

12. Composition for corrosion-resistant coating of metal parts according to claims 7 to 11, characterized in that it includes an organic solvent in an amount of from 1 to 30 wt.% in relation to the weight of the entire composition.

13. Composition for corrosion protection of the metal detail is second to item 11, characterized in that the organic solvent is a glycol ether, in particular diethylene glycol, triethylene glycol and dipropyleneglycol.

14. Composition for corrosion-resistant coating of metal parts according to claims 7 to 13, characterized in that it contains 0.005 to 2 wt.% thickener, specifically a derivative of cellulose, more specifically hydroxymethylcellulose, hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, xanthan gum or related thickener polyurethane or acrylic type.

15. Composition for corrosion-resistant coating of metal parts according to one of claims 7 to 14, characterized in that it contains from 3 to 20 wt.% silane.

16. Composition for corrosion-resistant coating of metal parts according to one of claims 7 to 15, characterized in that the silane consists of γ-glycidoxypropyltrimethoxysilane.

17. Composition for corrosion-resistant coating of metal parts according to one of claims 7 to 16, characterized in that the organic solvent contains, in addition, up to about 10 wt.% white spirit.

18. Corrosion-resistant coating of metal parts, characterized in that it is obtained from the composition for coating according to one of claims 7 to 17 by spraying, dipping or immersion with the rotation, and the coating layer is subjected to curing, prepact the tion carried out at a temperature of from 70 to 300° C.

19. Corrosion-resistant coating of metal parts on p, characterized in that the curing is carried out for about 30 minutes

20. Corrosion-resistant coating of metal parts according to claim 19, wherein before curing metal with the coating being dried, preferably at a temperature of about 70°C for approximately 20 minutes

21. Corrosion-resistant coating of metal parts according to one of p-20, characterized in that it is applied on the metal parts to be protected, in a layer thickness of from 3 to 15 μm and preferably a thickness of from 5 to 10 microns.

22. A metal substrate coated with an anticorrosive coating according to one of PP-21.



 

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