Anticorrosive pigments

FIELD: metal-protecting materials.

SUBSTANCE: invention relates to protection of metals against corrosion using paint and varnish coatings. Invention proposes using as anticorrosive pigments co-precipitated manganite-phosphates, manganite-silicates, manganite-sulfates of metals of the general formula: MMnOxnMZ wherein M means Ca2+, Zn2+, Fe2+, Sr2+ at Z - PO43-, SiO32-, and M means Ba2+ at Z - SO42-, PO43-, SiO32-; x = 2.5-3; n = 0.5-10 with the content of co-precipitated manganite of corresponding metal from 5 to 70 wt.-% as anticorrosive pigments. Proposed pigments by their anticorrosive properties exceed that of zinc tetraoxychromate. Invention provides applying low toxic anticorrosive pigment-inhibitors with protective properties comparable with that of chromate pigments.

EFFECT: expanded assortment of anticorrosive pigments.

1 tbl

 

The invention relates to the field of protecting metal from corrosion paints.

It is known that the main protective function in the system of coatings on metals perform primers, anti-corrosive action of which is largely determined by the content and type of pigments. The most effective in this aspect are anti-corrosive pigments and inhibitors present in the coating composition can suppress corrosion processes even in violation of their integrity. However, the most widely used pigments of this type (chromium and lead) are highly toxic. Enhancing the environmental soundness of the materials used for coatings in the past decade, the priority directions of development of the paint industry in future.

The first connections among used to reduce the toxicity of anti-corrosive coatings instead of chromium and lead were phosphates.

As phosphate-containing pigments are mainly used phosphates of zinc and chromium, which are non-toxic crystalline [see the book of Korsun L. F., Kalin T.V., S. Stepin. Inorganic pigments. Ref, ed. - SPb.: Chemistry, 1992. - 336 S.]. The zinc phosphate Zn3(PO4)· nH2O little soluble in water, but Les is to soluble in acids. Phosphate chromium CR(RHO4)· mo2About practically insoluble in water, resistant to acids and alkalis. Phosphate chromium is not used as an independent anti-corrosive pigment. It is used in pigment compositions, in particular in chromate.

At the present time to protect metals from corrosion is known the use of condensed phosphates of metals - diphosphate copper si2P2O7, calcium CA2P2O7magnesium Mn2P2O7; polyphosphates of the calcium CA3(R3About10)2·1,5H2O, zinc Zn3(R3About10)2·H2O, aluminum Al3(R3About10)2·2H2O; collateralisation iron Fe2P4O12, copper Cu2P4O12, Nickel Ni2P4O12, zinc Zn2P4O12magnesium Mg2P4O12, calcium Ca2P4O12and manganese Mn2P4O12[see AC Czechoslovakia, 262501, 256138, 259337, 247844, 253098, 259926, 245071, 259906, 260487, 259341; Zotov E.V., Luganceva L.N., Petrov LN. The protective properties of a number of passivating pigments // Paint-and-lacquer materials and their application. - 1987. No. 5.- P.27-29].

The General lack of phosphate pigments used in anti-corrosive coatings, is the low efficiency in the initial stages razvitiepozvonochnyh corrosion process, which is related to their low solubility [Wienand H., Ostertag W. Anorganische Korrosionsschutzpigmente-Uberblick und neuere Entwicklung // Farbe und Lack. - 1982. Bd.88. No. 3. -S.183-188].

Another group of anti-corrosion pigments are ferrites are mixed oxides of the spinel structure of the General formula MeO-Fe2O3where Me is magnesium, zinc, tin, copper, calcium, cadmium, cobalt, barium, strontium, iron, manganese [see the book of Korsun L. F., Kalin T.V., S. Stepin. Inorganic pigments. Ref, ed. - SPb.: Chemistry, 1992. S.138]. Ferrites can be regarded as a ferrous salt acid HFeO2. However, the ferrites on the protective properties inferior to lead and chromate pigments.

Known application as anticorrosive pigments compounds manganese - manganites metals General formula Rn3where R - Ca2+Zn2+, Fe2+, Sr2+(patent RF №2216560, application No. 2001109129/04(009512) from 05.04.01, IPC 7 09 D 5/08). Manganites are less toxic and their protective properties are not inferior to chromate pigments.

The disadvantage of these compounds is their relatively high solubility, which leads to deterioration of the insulating properties of coatings based on them.

Thus, up to now a full-fledged alternative to toxic pigments, effectively protecting metals from corrosion, is not found. Therefore, still remains an actual problem is and search low-toxic pigments, for anti-corrosive effect is not inferior to chromate.

The objective of the invention - expanding Arsenal of low-toxic anticorrosive pigments inhibitors, protective properties are not inferior chromatin pigments.

The problem is solved by the application as anticorrosive pigments soosazhdennykh the manganite-phosphate, manganite-silicates, manganite-sulfates of metals of the General formulacontent soosazhdenie of manganite suitable metal of from 5 to 70 wt.% as anti-corrosive pigments.

Proposed substances get by known methods based on the reduction reaction of permanganates to manganites in the presence of salt-forming metal ions (Kind of DEATH, of Oxygen compounds of manganese. M.: Academy of Sciences of the USSR. 1952, p.194), which used CA, Zn, Fe, Sr, Ba, followed by coprecipitation salts obtained from sulphates, phosphates and silicates of alkali metals.

For example, as a reducing agent can be used nitrite ion:

2MnO4-+3NO2-+2(n+1)Ba2++2nSO4-2(BaMnO3·nBaSO4)↓ +3NO-

The table presents the obtained pigmenti the results of their tests.

Example of receipt. Take 20%solutions of potassium permanganate, sodium nitrite, barium nitrate, sodium sulfate (ratio of the initial reaction 2MnO4-+3NO2-+6Ba2++4SO4-2(BaMnO3·2BaSO4)↓ +3N3-), poured into one container and stirred until the discoloration of the mother liquor. The precipitate is washed, filtered and dried to constant weight at 120° C. the resulting pigment of formula Wampo3·2SO4is a brown powder with a content of mn containing substances 34% (example 2, table).

Other pigments receive similarly, varying the source components in the range indicated in the claims. The ratio between the original components are calculated by the reaction depending on the number of mn containing substances in the final product.

The resulting products are highly dispersed powders brown and purple colors of different intensity and hue. An important difference from other mn containing substances is significantly lower toxicity, as the share of the mn containing substances in the investigated compounds is 5-70%. It should be noted that the MPC mn containing compounds comprised the focus of 0.3 mg/m 3and it is 30 times greater than the corresponding characteristic of chromate pigments.

For evidence of corrosion properties of the synthesized pigments have investigated the interaction of their aqueous extracts and water extracts of pigmented films with steel. As a comparison object used tetrachromat zinc relating to the most widely ispolzuemyi in practice chromium anticorrosive pigments.

The methodology of the tests.

Anticorrosive properties of the pigments was evaluated by examining the ability of aqueous extracts to slow down the corrosion of steel.

For the preparation of aqueous extracts about 15 g of the pigment is placed in a chemical glass with a capacity of 150-300 ml, poured 50 ml of distilled water, heated to boiling and boiled for 30 minutes, the Suspension is cooled, the filtrate is poured into the cylinder and bring the volume to 50 ml with distilled water, then mixed with an equal volume of 6%NaCl (Iagellonicae, Day, Iautomate. Laboratory pigments and pigmented paints, varnishes and lacquers, 1990, L.: Chemistry, s).

Surface preparation of samples of body steel 08KP before the corrosion test was carried out by blasting and subsequent degreasing mineral spirits and acetone.

As the e criterion anticorrosive properties of aqueous extracts of pigments used the value of the electrochemical potential (E) and the amount of current corrosion steel (Ik), in contact with 3%aqueous solution of sodium chloride. The electrochemical potential of the steel was measured relative to silver chloride electrode using the appliance pH-340, then the expected value of the potential relative to the normal hydrogen electrode.

The amount of current corrosion was determined by mathematical treatment of polarization curves of steel produced using a potentiostat PI-50-1 in the field of deviation E from -40 mV to +40 mV relative to the steady-state potential corrosion. Current corrosion was calculated by computer solution of the equations Wagner-Traud describing the corrosion process, method of successive approximation using the obtained experimental data:

i=ik[exp(2,3 Δ E/ba) - exp(2,3 Δ E/bk)], where (ikthe current density corrosion; babk- constant Tafes; Δ E - polarization specimen, mV; i - current density, polarization (Iagellonicae, Day, Iautomate, Laboratory pigments and pigmented paints, varnishes and lacquers, 1990, L.: Chemistry, p.189-190).

To assess the state of steel (passive or active) at a given value of E (by Pourbaix diagram) measured pH of the medium in contact with the metal, with the help of the device pH-340.

The results of the experiments are given in the table.

Held spymania showed synthesized pigments for anti-corrosive properties exceed tetrachromat zinc.

Application soosazhdennykh the manganite-phosphate, manganite-silicates, manganite-sulfates of metals of the General formulacontent soosazhdenie of manganite suitable metal 5 to 70 wt.% as anti-corrosive pigments.



 

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