Method for phosphatatizing of rusty iron-containing surfaces

IPC classes for russian patent Method for phosphatatizing of rusty iron-containing surfaces (RU 2261938):

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 of a titanium alloy surface phosphatization / 2255139

Method for phosphatatizing of rusty iron-containing surfaces / 2261938

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FIELD: varnish-and-paint industry and corrosion protection.

SUBSTANCE: 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%.

EFFECT: enhanced adhesion of phosphate film to metallic substrate and lacquer coating, and lowered treatment temperature to ambient temperature value.

2 dwg, 1 tbl, 3 ex

The invention relate to chemical treatment of iron-containing surfaces and preferably to the phosphating these surfaces before applying them to the conventional conversion coatings, such as paint or varnish.

The main structural material for the manufacture of various engineering products, including automotive, are iron-containing alloys, which under the action of various physical and chemical processes during their operation corrosion - rust. The presence of rust on the surfaces of ferrous alloys is characterized by the formation of the hydroxides and oxides of iron.

Traditionally subjected to rusting of the surface before applying them to the various conversion coatings (lacquer, paint) phosphatherium. To this end metalloproteinase treated with aqueous solutions of the compositions, the components of which interact with the hydroxides and oxides of metals, modifying them into an insoluble and inactive corrosion in the connection with the formation on the surface of the phosphate layers (films).

As the modifying composition use composition containing inorganic and organic acid (orthophosphoric acid (H₃PO₄), nitrilotriacetate and others). Thus preferably the use of water is of astora free phosphoric acid, which in the interaction at room temperature with rust forms insoluble iron phosphate, the main distinguishing feature of which is the chemical protection of the metal from penetrating influence of oxygen.

Formed by the interaction of orthophosphoric acid with the hydroxides and oxides of iron phosphate is formed on the surface of the metal phosphate film. However, from this case, the protective phosphate film has an amorphous structure, not having sufficient adhesive strength with respect to the basis of metalloproteinase. Low adhesive strength of the formed phosphate coating reduces the effectiveness and subsequent conversion coatings (paints and varnishes), applied to metalloproteinase.

In these circumstances the most effective for phosphating of iron-containing surfaces of aqueous compositions, containing a mixture of phosphates of manganese and iron. The most common is an aqueous solution composition containing salt "mage" (a mixture of acid salts, respectively dihydrophosphate manganese (Mn(H₂PO₄)₂), iron Fe(H₂PO₄)₂) and water. When interacting specified an aqueous solution of iron-containing surfaces of the dissolution occurs on the treated surface of iron and release of hydrogen, and n is the treated surface is formed a protective layer of phosphate of manganese and iron in the crystal structure.

However, the process of film forming phosphating in this case involves the use of an aqueous solution of the composition at the temperature of the solution, preferably not less than 100°C.

To improve the activity of known composition on the basis of salt "mage in aqueous solution it is introduced accelerators, in particular soluble in the acidic environment of the zinc compounds, which reduce external energy phosphate (see kN. "Corrosion", the authors Istamulova etc., S.-Petersburg: Hemostat, 2000, str-326).

However, the use of zinc salts in the phosphatizing metalloproteinases environmentally inappropriate under the terms of the subsequent disposal of waste.

There is a method of phosphating iron surfaces by treating them with a composition containing salt "mage", zinc nitrate, sodium fluoride, sodium carbonate, surface-active substance in the form of a₇-C₁₀performancereport sodium, potassium, manganese or zinc (see patent SU # 1723195, With 23 22/73, 1992).

Treatment of iron-containing surfaces is approximately 9% aqueous solution of the aforementioned composition. The method of phosphating in U.S. Pat. No. 1723195 selected as the closest analogue of the proposed technical solution.

The effectiveness of the known phosphating process is achieved accounts the external energy field, to heat the processing solution to a temperature not less than 55°and in the presence of a known composition in addition to salt, "mage" (a mixture of acid salts, respectively dihydrophosphate manganese (Mn(H₂PO₄)₂), iron Fe(H₂PO₄)₂) multicomponent catalyst, such as zinc nitrate, sodium fluoride, sodium carbonate, surfactant (C₇-C₁₀performancereport sodium, potassium, manganese or zinc). The processing of ferrous surfaces with an aqueous solution of the composition is carried out at akanani products in solution in the processing composition and at elevated temperature (not less than 55° (C)that increases the external energy costs and technological limits the possibilities of use of the composition for treatment of geometrically-complex surfaces and surfaces of large-size products, parts, characteristic, for example, for the automobile industry. The complexity of known composition increases the expense of manufacture.

For these reasons, the processing of ferrous surfaces in contact impact zone rust aqueous solution of the composition ineffective. The inefficiency of the contact impact zone rusting of iron-containing surfaces is explained including insignificant to the number of phosphate ions (P ₂O₅) in aqueous solution.

Thus, there is a method of phosphating is technologically limited capabilities and cannot be used in the phosphating separate areas of rust on geometrically-complex surfaces and large-sized products, parts, characteristic, for example, for the automobile industry.

The objective of the proposed technical solution is to provide a method for phosphating of iron-containing surfaces with rust composition, ensuring implementation of the technical result for the effective formation of the phosphate film subjected to the rust area of a surface.

The objective of the proposed technical solutions were also involved in the technical implementation of the efficient formation of the phosphate film on the treated iron rich surface by using for this purpose the composition having low (room) temperature at the contact impact on the manufacturing area of a surface.

The objective of the proposed technical solutions were also involved in the technical implementation of the efficient formation of the phosphate film on the treated iron rich surface when used for this purpose, aqueous solution with an optimal composition of the components, ensuring the formation of the microcrystalline structure of the FOSFA is based films in the area of processing, regardless of the macro - and microstructure zones rust.

This object is achieved in that in the method of phosphating iron surfaces with rust, consisting in the use of the composition containing salt "mage", surfactant and water, according to the invention as a surfactant is used as a compound (A) General formula:

in the following ratio, wt.%:

Sol "Mage"	5-9
The compound (A)	0,1·10^-2-0,5·10^-2
Distilled water	rest

When iron phosphating surfaces of the inventive method using an aqueous solution of the composition indicated composition and component wt.% the ratio of them subjected to the rust area of a surface in contact influence of the processing composition is effective formation of the microcrystalline structure of the phosphate film. The process is carried out without external energy cost of processing solution. The efficiency of formation of the microcrystalline structure of the phosphate film in the area of surface rust due to the ionic activity of phosphate in solution and energy activities used in the composition of the surfactant in the form of a connection is possible (A). Use in the inventive method, the aqueous phosphating solution with the compound (A)having an active cations fluorocarbons contribute to intensify the process of crystallization of phosphates on the macro - and micro-level structures of rust on the treated area of a surface.

When implementing the proposed method phosphating ferrous surfaces with typical manifestation of rust on the treated surface is formed of a phosphate film metallovedeniye microcristalina patterns having high adhesion to the metal base and provide good traction subsequent conversion coatings (paints, lacquers) with this basis.

In the analysis of the prior art are not identified ways of processing ferrous surfaces with rust aqueous solutions of the compounds with the combination and ratio of components in them, corresponding to the claimed technical solution and implement the above technical result that indicates the presence of the claimed technical solution of novelty and inventive step, which was to be proved below is a description.

When implementing the proposed method it is established that the use of the implementation of the composition with the claimed composition components and value them the most is now. The changing composition of the components and their ratios will either lead to a deterioration in the quality of formed on the treated surface of the phosphate film, or will not improve the properties of the latter.

The essence of the invention is illustrated recommendations regarding the selection of raw materials, examples of specific compounds, the recommendations of their practical application and results of the tests.

To clarify the essence of the invention provides the following graphics:

figure 1 shows the obtained electron microscope image of the crystal structure of the phosphate film obtained by treatment zone rusting of iron containing surface with an aqueous solution of the composition according to the control method;

figure 2 presents obtained using electron microscope image of the crystal structure of the phosphate film obtained by treatment zone rusting of iron containing surface with an aqueous solution of the composition according to the present method;

Table - test results phosphate films obtained at the contact impact zone rusting of iron-containing surfaces of aqueous solutions of the compositions of examples 1 and 2.

For the manufacture of a particular aqueous solutions of the compositions used for carrying out the invention, use ready-to-use raw materials and p is edocfile industrial output:

Sol "Mage" in the form of a mixture of dihydrophosphate manganese (Mn(H₂PO₄)₂and dihydrophosphate iron (Fe(H₂PO₄)₂) - THE 6-09-02-570-2000; zinc nitrate (Zn(NO₃)₂·6N₂O); phosphoric acid (H₃PO₄); sodium carbonate (Na₂CO₃); sodium fluoride (NaF);₇-C₁₀- performancereport sodium.

The compound (A), preferably trademark "Platonic K-76". Fluoride surfactants Platonic K-76" - waxy product from light yellow to brown in color, soluble in water and alcohols. The density of 1.56 g/cm³.

For implementing the method of phosphating ferrous surfaces and confirm the effectiveness of the proposed method of the above raw materials by the method of mixing were prepared with the following aqueous solutions:

Example 1 - the composition according to the present method:

Sol "Mage" - 8,24 g; compound (A) - 0.003 g; distilled water - 100 ml

Example 2 - composition by a known method (patent 1723195):

Sol "Mage" - 3.5 g; zinc nitrate is 5.98 g; sodium fluoride - 0,6·10^-3; sodium carbonate - 0,01 g; C₇-C₁₀- performancereport sodium - 0,01 g; distilled water - 100 ml

Example 3 and control structure

Orthophosphoric acid (H₃PO₄), ρ 1.7 g/cm³- 5,1 ml; water distil the new - 100 ml.

In the preparation of these compositions in examples 1-2, the process of mixing was carried out in the sequence: in distilled water were added salt "Mage" and these examples 1-2 components are mixed at a temperature not exceeding 70°C for 10-20 min to obtain the aqueous acidic solution. The specified temperature improves the process of dissolution of salts.

To confirm the efficiency of the method of phosphating ferrous surfaces according to the invention were conducted evaluation tests of aqueous solutions of the compositions in examples 1-3 according to the following procedure:

iron-containing samples with a total surface area of the handle 25 cm²and with area formed on them rust up to 45% of pre-cleaned from dirt and obezzhirivatel detergent;

zone rusting surfaces of the samples by the method of contact exposure, mainly using brushes were applied aqueous solutions of the compositions in examples 1-3;

excerpt processing specified zones of the surfaces was 7 min for all the samples;

the temperature of the processing of aqueous solutions of the compositions is not more than 25°C.

Obtained by processing these aqueous solutions of the compositions of the surfaces of the samples after drying were evaluated according to the quality of the formed phosphate coats.

is the valuation of the quality of a phosphate coating layers (phosphating) in the tested samples, treated with solutions of examples 1 and 2 was carried out according to the following criteria:

determination of the mass of the phosphate layer (g/cm²by weighing the test specimens prior to phosphating and after phosphating areas of rust on the surfaces GOST 9.402-80;

determination of the corrosion resistance of phosphate coatings on drip method Akimov - GOST 9.302-88;

determination of the corrosion resistance of phosphate coatings after application to it of the paint coating by immersing the dyed samples in 3%sodium chloride solution until the first outbreak of corrosion - GOST 20811-75.

The test results are summarized in table.

Evaluation of the quality of a phosphate coating on the test samples treated with solutions of examples 1 and 3 was performed using an electron microscope to determine the crystal structure of phosphate films (layers)obtained when processing zones rusting surfaces of samples 1 and 2.

To confirm the obtained results and their comparability in the table as well as test data by the present method and known (Pat.) when using aqueous solutions of examples 1 and 2 in the processing of ferrous surfaces of the samples by the method of dipping in the respective solutions, the temperature of which is not more than 25°C.

From these tests the following table is the duty to regulate, while implementing the method of phosphating ferrous surfaces according to the invention the corrosion resistance of the formed phosphate layer as the basis of the processed metalloproteinase, and in relation to deposited on this surface coatings used in the most effective unlike similar results according to the method of phosphating. These circumstances are explained by the efficiency of the mass increase of the phosphate layer formed in the treatment zone of iron containing surface, and microcrystalline structure it formoobrazovanija.

The invention can find application in various industries that use the products and parts manufactured on the basis of iron alloys. The most effective use of the claimed invention of the method of phosphating iron surfaces with rust for maintenance and repair of vehicles with specific bodies of geometrically-complex structure surfaces with separate pockets of rust.

The method of phosphating iron surfaces with rust.
Aqueous solutions of the compositions according to examples	the mass of the phosphate layer (g/cm²)	the corrosion resistance of phosphate covered what I min. initial/after 72 hours.	the corrosion resistance of the paint coating on the phosphate layer, day.
Example 1 (contact exposure to the treated area rusting of iron containing surface)	0,041	8/4	9
Example 2 (contact exposure to the treated area rusting of iron containing surface)	0,03	7/2	6
Example 1 (when akanani test sample)	0,046	9/5	10
Example 2 (when akanani test sample)	being 0.036	7/3	7

The method of phosphating iron surfaces with rust, consisting in the use of the composition containing salt "mage", surfactant and water, characterized in that the surfactant is used as a compound (A) General formula:

in the following ratio, wt.%:

Sol "Mage"	5-9
The compound (A)	0,1·10^-20,5·10^-2
Distilled water	Rest