Method of a titanium alloy surface phosphatization

IPC classes for russian patent Method of a titanium alloy surface phosphatization (RU 2255139):

C23C22/36 - containing also phosphates

Another patents in same IPC classes:

Method of a titanium alloy surface phosphatization / 2255139

The invention is pertaining to the methods of chemical treatment of titanium alloys surfaces, in particular, to the methods of treatment of titanium alloys surfaces for improvement of their adhesiveness for lacquer coatings (LC) and may be used in various industries, including aircraft, space, motor-car industry, shipbuilding, construction and architecture, etc. where titanium alloys with decorative coloring are applied. The method provides for degreasing, water flushing, phosphatization of a titanium alloy surface using treatment with a water solution containing ions of zinc, ions of phosphate, ions of nitrate, a repeated water flushing and drying. At that before the phosphatization a titanium alloy surface is treated with an oxidation solution on the basis of a mixture of nitrogen and etching acids or magnesium oxide. The solution for phosphatization is additionally introduced with ions of sulfate, ions of fluorine and ions of tartrate at following ratio of components, g/l: PO₄ ^-3 4.0-75.0, Zn⁺² 3.0-16.0, SO₄ ^-2 2.07.0, NO₃ ^-1 41.0-206.0, F^-1 1.0-3.5, (C₄H₄O⁶)^-2 1.8-9.0. The technical result is an increased adhesive capability of a titanium alloy surface for application of the lacquer coatings without hydrogenation of the surface.

Method for phosphatatizing of rusty iron-containing surfaces / 2261938

Phosphatatizing of rusty iron-containing surfaces before applying lacquer coatings involves formulation containing 5-9% of salt "Majef", 0.1·10-2-0.5·10-2 % of compound having following formula: , and distilled water to 100%.

Titanium alloy surface phosphatization method / 2299268

Invention relates to chemical treatment of titanium alloy surfaces and can be used in aircraft, spatial, and automotive industries, in ship building and other industrial fields. Method comprises degreasing, water rinsing, and phosphatization of titanium alloy surface with composition containing, g/L: PO₄ ^-3 4.0-75.0, Zn⁺² 3.0-16.0, SO₄ ^-2 2.0-7.0, NO₃ ^-1 41.0-206.0, F^-1 1.0-3.5, (C₄H₄O₆)^-2 1.8-9.0, and ultrafine polytetrafluoroethylene 800-1000.

Metal material with treated surface without using chromate / 2387738

Invention relates to metal material with treated surface free from chrome. Metal material has the surface to which there applied and dried is water-based matter so that composite coating is obtained. Water-based matter includes silica-containing organic compound (W) obtained by mixing silaned binding substance (A) containing one amine group in molecule/and silaned binding substance (B) containing one glycidyl group in molecule, at weight ratio of solid matters [(A)/(B)] 0.5- 1.7, and the molecule of which has at least two functional groups (a) of the formula -SiR¹ R² R³, in which R¹, R² and R³ represent alkoxyl group or hydroxyl group; at least one represents alkoxyl group and one or more at least of the same type of hydrophilic functional groups (b) chosen from hydroxyl group which is different from the group, which can be included in functional group (a)and amine groups with molecular-weight average of 1000-10000, at least one fluor compound (X) chosen from fluorotitanium acid or fluorozirconium acid, phosphoric acid (Y), and vanadium compound (Z). Weight ratio of solid matters [(X)/(W)] of the coating is 0.02 - 0.07, [(Y)/(W)] is 0.03- 0.12, [(Z)/(W)] is 0.05- 0.17, and [(Z)/(X)] is 1.3- 6.0.

Chromium-free passivation of steel / 2396370

Invention refers to application of coating on metal surface. The procedure for application of conversion or passivated coating on surface of galvanised steel and steel galvanised by hot immersion consists in interaction of said steel with a water treating composition containing film-forming latex polymer including acrylate resin, fluorine-containing acid, phosphorus acid and non-ionogenic polymer surface active substance containing block copolymer of poly-oxy-ethylene/oxy-propylene. Composition for forming conversion or passivated coating contains from 0.01 to 50 wt % of film-forming latex polymer and from 0.01 to 40 wt % H₃PO_4, from 0.01 to 30 wt % of fluorine containing acid, from 0.01 to 20 wt % of poly-oxy-ethylene/oxy-propylene block copolymer, water - the rest, wherein the said composition equals to 100 wt %.

Procedure for coating metal surface with water composition containing silane-usilanol/siloxane/polysiloxane and said composition / 2402638

Procedure consists in coating metal surface with composition containing a) at least one compound a) chosen from silane, silanol, siloxane and polysiloxane at contents of silane/ silanol/ siloxane/polysiloxane from 0.02 to 1 g/l in terms of base of corresponding silanol and b) at least two compounds b) chosen from compounds containing titanium, hafnium, zirconium, aluminium or/and boron at contents of compounds b) from 0.1 to 15 g/l in terms of sum of corresponding metals and at least two complex fluorides chosen from complex fluorides of aluminium, boron, titanium, hafnium and zirconium, and also at least one kind of cations chosen from cations of metals of 1-3 and 5-8 subgroups including lanthanides, and also of the 2-nd basic group of periodic table of the elements or/and at least one corresponding compound c) at their contents from 0.01 to 6 g/l, d) at least one organic compound chosen from monomers, oligomers, polymers, copolymers and bloc-copolymers, also weight ratio of compounds a) to organic compounds d) in terms of additive of solid substance in the composition is from 1:0.05 to 1:12 depending on amount of added organic compound d) or/and e) at least one substance influencing pH value and f) water.

Method of applying coating on metal surface by treating with aqueous composition, aqueous composition and use of coated metal substrates / 2418885

Metal surface is treated with an aqueous composition containing a) at least one compound a), selected from silanes, silanols, siloxanes and polysiloxanes, where content of silane/silanol/siloxane/polysiloxane in the composition is between 0.005 and 80 g/l, based on the corresponding silanols, b) at least one compound b), containing titanium, hafnium, zirconium, aluminium and/or boron, from which at least one is a complex fluoride, where the composition contains the compound b) in amount of 0.1-5 g/l, based on the sum of the corresponding metals, c) at least one type of cations selected from cations of metals of subgroups 1-3 and 5-8, including lanthanides, as well as group II elements and/or at least one corresponding compound c), where content of cations and/or corresponding compounds c) in the composition is between 0.01 and 6 g/l, at least one substance d) selected from d₁) silicon-free compounds, having at least one amine group, one urea group and/or one ureide group, d₄) phosphorus-containing compounds, anions of at least one phosphate and/or anions of at east one phosphonate, and e) water, where the aqueous composition is free from organic polymers.

Solution of phosphatisation with hydrogen peroxide and chelate forming carbonic acids / 2428518

Acid water solution for phosphatisation contains from 0.2 to 3 g/l of ions of bivalent zinc, from 3 to 50 g/l of ions of phosphate in terms of PO^3- ₄, from 15 to 50 mg/l of hydrogen peroxide or equivalent amount of substance removing hydrogen peroxide, from 0.5 to 1.0 g/l of one or several aliphatic chelate forming carbonic acids containing from 2 to 7 of carbon atoms with maximal one point of contents of free acid.

Thermally cured corrosion-resistant agent not containing chrome / 2454486

Agent with pH of 1 to 3 is intended to be applied as primary coating on metal substrates and contains water, as well as a) ions of fluorine complexes of titanium and/or zirconium, b) at least one corrosion-protective pigment, c) at least one water-soluble or water-dispersed polymer in the above pH range, which has pH 1-3 in water solution with concentration of 50 wt %. At that, c) includes i) links at least of two different ethylenically unsaturated monomers chosen from the group including acrylic acid, methacrylic acid, composite esters of acrylic acid and composite esters of methacrylic acid; at that, at least one monomer is chosen from the group including composite esters of acrylic acid and composite esters of methacrylic acid, and ii) 0.5 to 4.0 mol % of monomeric links with groups of phosphoric acid or ester of phosphoric acid. Application method of coating on metal strip involves application of the above agent of such thickness so that a coating with thickness of 0.5 to 10.0 mcm is formed as a result of its curing performed by heating of metal strip to the temperature of not more than 150°C during not more than 60 seconds.

Zirconium- and titanium-bearing phosphating solution for passivation of metal composite surfaces / 2464356

Water composition contains 5-50 g/l of phosphate ions, 0.3-3 g/l of zinc (II) ions, 1-200 ppm chosen from water-soluble zirconium and titanium compounds, in terms of elementary zirconium and titanium; at that, one or several water-soluble compounds of zirconium and free fluoride is contained in quantity of 1-400 ppm, which is measured with an electrode sensitive to fluoride. In corrosion-protection conversion treatment method of metal surfaces, which, in addition to steel and/or zinc-plated steel and/or alloyed zinc-plated steel surfaces, also contain aluminium surfaces, cleaned and degreased metal surfaces are brought into contact with water composition.

FIELD: aircraft industry; space industry; motor-car industry; shipbuilding; construction industry; chemical treatment of titanium alloys surfaces.

SUBSTANCE: the invention is pertaining to the methods of chemical treatment of titanium alloys surfaces, in particular, to the methods of treatment of titanium alloys surfaces for improvement of their adhesiveness for lacquer coatings (LC) and may be used in various industries, including aircraft, space, motor-car industry, shipbuilding, construction and architecture, etc. where titanium alloys with decorative coloring are applied. The method provides for degreasing, water flushing, phosphatization of a titanium alloy surface using treatment with a water solution containing ions of zinc, ions of phosphate, ions of nitrate, a repeated water flushing and drying. At that before the phosphatization a titanium alloy surface is treated with an oxidation solution on the basis of a mixture of nitrogen and etching acids or magnesium oxide. The solution for phosphatization is additionally introduced with ions of sulfate, ions of fluorine and ions of tartrate at following ratio of components, g/l: PO₄ ^-3 4.0-75.0, Zn⁺² 3.0-16.0, SO₄ ^-2 2.07.0, NO₃ ^-1 41.0-206.0, F^-1 1.0-3.5, (C₄H₄O⁶)^-2 1.8-9.0. The technical result is an increased adhesive capability of a titanium alloy surface for application of the lacquer coatings without hydrogenation of the surface.

EFFECT: the invention ensures an increased adhesive capability of a titanium alloy surface for application of the lacquer coatings without hydrogenation of the surface.

2 tbl, 1 ex

The invention relates to chemical surface treatment of titanium alloys, in particular to a method of surface treatment of titanium alloys to improve adhesion for paint (LCP), and can be used in various industries, including aerospace, automotive, ship building, construction and architecture, etc. using titanium alloys with decorative painting.

It is known that titanium alloys due to high passiviruemost them in atmospheric conditions, especially with high humidity, have a very low level of adhesion to various materials. In this regard, put on them paintwork in the operation of products in different climatic conditions often delaminated titanium alloys and products lose their decorative appearance. Therefore, before applying the paint coating on the surface of the titanium alloy to be put on her, the intermediate layer having high adhesion to the metal surface and paint finishes.

A method of obtaining a phosphate coatings with high adhesion and high corrosion resistance, for which the metal surface is subjected to a cathodic electrolytic treatment at a low temperature the solution, containing phosphate ions and other anions and ions powdered metal. The ratio of phosphate ions to all other anions is 0.6 and 0.08 (Japan's Bid No. 2-163098).

Due to the presence of a large number of active ions is significant etching of the metal which increases adhesion of the resulting phosphate coating.

However, the resulting phosphate coating and electrolytic method of its application may not be used for surface preparation of titanium alloys under LCP, as it does not have the level of adhesion no paintwork or titanium alloy.

The known method of forming a phosphate coating on the steel surface, which is in the process of continuous processing of steel sheet with an aqueous solution containing ions of the hydroxy acid type, phosphoric, nitric, metal ions of the type of zinc and as an oxidizer ions nitrous acid. The temperature of the treatment solution is maintained in the range of 0-40°With (Application of Japan No. 3-59989).

The known method does not allow adhesion layer on the surface of titanium alloy under LCP.

There is a method of coating articles made of titanium or titanium alloy, which requires the use of an aqueous solution containing fluoride ions and ions of one or more metals from the group consisting of magnesium, calcium, Marg is the end, iron, cobalt, Nickel, zinc and molybdenum, and the pH of the solution exceeds 1.5. The method differs in that the surface of the product contains 5-40 g/l fluorides, nitrates, sulfates at least one metal from the group comprising magnesium, calcium, manganese, iron, cobalt, Nickel, zinc and molybdenum, the one substance from the group of organic chelating agents, in an amount of 0.1-2 g/l, the water-soluble organic polymer in an amount of 0.1-10 g/l and a surfactant in an amount of 0.01-3 g/l (Germany Application No. 3816557).

The disadvantage of this coating is that it does not have the level of adhesion for coatings.

Closest to the invention to the technical essence and the achieved result is a method for phosphating the surface of the alloys under LCP, which includes degreasing alkaline detergent composition, a rinse water temperature of 20°C), phosphate coating by dipping in concentrated solution, containing:

Zn⁺²0,3-4,8

NO₃ ^-10,2-10

Ni⁺²0,03-1,2

P₂O₅1,5-19

levulin acid of 0.001 to 0.2

ClO^-1 ₃0,01-1,5

isatin is 0.0002-a 0.1

water the rest, at a temperature of 45-65°

repeated washing at a temperature of 20°passivation solution SGAs₃, drying at a temperature of 100° (RF Patent No. 1465465).

The solution is designed to improve interviewer the precise resistance of phosphate coatings complete with LCP. The disadvantage of this method is that its application for phosphating of titanium alloys is not possible to ensure the adhesiveness of the surface of Titan to the LCP due to the presence in the solution components that Passepartout the surface of the titanium alloy.

The technical object of the present invention is to provide a method for phosphating the surface of the titanium alloy, which enables to increase the adhesive power of titanium alloy under LCP without hydrogenation of the surface.

To solve this problem, a method for phosphating the surface of the titanium alloy, including degreasing, washing with water, phosphating the surface of the titanium alloy by treatment with a solution containing zinc ions, phosphate ions, nitrate ions, re-washing and drying, characterized in that prior to phosphating the surface of the titanium alloy is treated with an oxidizing solution based on a mixture of nitric acid and hydrofluoric acid or magnesium oxide, and the solution for phosphating impose additional sulfate ions, fluorine ions and tartrate ions in the following ratio of components (g/l):

Zn⁺²3-16

RHO₄ ^-34,0-75

NO₃ ^-141-206

SO₄ ^-22,0-7,0

F^-11,0-3,5

(C₄H₄O₆)^-21,8-9,0

at this pH, the support is more in the range of 2.0 to 3.2.

The phosphating process is carried out at a temperature of 18-30°C.

In those cases, when the surface of the titanium alloy is impossible to enter into contact with aggressive oxidizing solution, instead use magnesium oxide. In this case, the surface of titanium alloy strip to a depth of 20-30 microns for removal of the natural oxide film.

Preliminary surface treatment of the titanium alloy in an oxidizing solution and the introduction of ions of sulfate, fluoride and tartrate in combination with Zn ion, phosphate and nitrate allows to obtain a phosphate film without hydrogenation of titanium alloy.

An example implementation

Samples of titanium alloy VT20 size 70×150×1.2 mm was degreased in a standard alkaline solution according to GOST 9.047-75. After washing in water, the samples were treated with an oxidizing solution in a mixture of nitric and hydrofluoric acid, and then subjected to phosphating at a temperature of 20°C for 2 hours, re-washing and drying with hot air. On the prepared surface was applied paint coating (painting: epoxy primer VG 28, drying 24 hours, and then the enamel With 21/100 UVR 2 layer, drying each layer 1 hour, then extract to test 7-10 days), after which the adhesion was determined. The wetting angle phosphated surface defined on the device ″Picus″.

Test algesiology according GOST and 15 140-78 method of lattice cuts before and after the test samples in distilled water for 14 days. When determining the adhesion of this method on the test area of the sample surface was done with a scalpel parallel incisions to metal length not less than 20 mm at a distance of 1, 2 or 3 mm from each other. A similar method was making incisions in the perpendicular direction.

As a result, the coating was formed in a lattice of squares of equal size. After applying the cuts to remove detached pieces of the coating on the surface of the pasted adhesive tape and removed the floor, if it was peeled off from the metal surface.

Table 1 shows the modes of surface treatment of titanium alloy and mortar compositions, where the example 1-3 - proposed method, example 4 prototype.

Table 2 shows the influence of the composition of the phosphating solution on the degree of hydrogenation of the surface alloy W 20.

Because titanium alloys are very sensitive to navodorozhivanie depending on the different types of chemical processing, table 2 shows measurement results of changes in the degree of hydrogenation of the surface alloy W 20 depending on the composition of the phosphating solutions.

It is known that one of the characteristics that define the adhesive ability of titanium alloys to other materials, is the wetting angle of the surface. Thus, the smaller the contact angle, the higher the adhesive is capable of being the feature of the material.

From table 2 it follows that after processing the surface of the alloy W 20 proposed method and the prototype method, the contact angle of the surface in the samples No. 1-3 significantly lower contact angle according to example 4, what characterizes a good adhesive ability of titanium alloy for QTL due to the proposed method.

Determining the amount of hydrogen in the surface layer of alloy W 20 conducted local spectral method according OST 1 900 34-81.

Table 2 also shows that the best results on hydrogen obtained on samples treated by the proposed method. The solutions proposed method does not cause hydrogen permeation alloy W 20 that is associated with a high concentration in the oxidizer solution, as the phosphating process is in the initial stage with a very small release of hydrogen, then the hydrogen evolution almost stops and then goes only film seal.

Surface finish alloy W 20 solution of the prototype method leads to navodorozhivanie surface above the norm specified in OCT'e 1 90013 (less than 0.015).

These results correlate well with the test samples with QTL in distilled water. The greatest number of days passed samples without peeling paint from a metal surface according to examples No. 1-3, while the sample according to example No. 4 was peeled off after 1 day, the I.

Thus, the proposed method will improve the adhesion ability of titanium alloys without hydrogenation of the surface that will make it possible to expand the area of application where the use of titanium alloys with decorative painting.

Table 2
The physical characteristics of the surface alloy W 20 depending on the composition of the phosphating solution
no solution	Hydrogen, mass%	The wetting angle, °	The duration of the test in distilled water without delamination boils from the surface, the day^*1
with the surface of the sample	after cleaning the surface to a depth of 30 microns
1	0,006	0,005	0	15
2	0,007	0,006	0	14
3	0,007	0,007	2	14
4	0,022	0,005	72	1
^*1 High adhesion is not less than 14 days on TH THE T 15140-78

1. The method of phosphating the surface of the titanium alloy, including degreasing, washing with water and phosphating the surface of the titanium alloy by treatment with a solution containing zinc ions, nitrate ions, phosphate ions, re-washing and drying, characterized in that prior to phosphating the surface of the alloy is treated with an oxidizing solution based on a mixture of nitric and hydrofluoric acids or magnesium oxide, and the solution for phosphating impose additional sulfate ions, fluorine ions and tartrate ions in the following ratio of components, g/l:

RHO₄ ^-34,0-75,0

Zn+²3,0-16,0

SO₄ ^-22,0-7,0

NO₃ ^-141,0-206,0

F^-11,0-3,5

(C₄H₄About₆)^-21,8-9,0

2. The method according to claim 1, characterized in that before processing the magnesium oxide surface of titanium alloy is subjected to mechanical grinding.

3. The method according to claim 1, characterized in that the temperature of the solution for phosphating is 18-30°C and pH 2.0 to 3.2.