The method of obtaining the composition and the way it handles its metal version

 

(57) Abstract:

As a result of heating water mixture such fluoride acid as H2TiF6and such an oxide, hydroxide and/or carbonate, as silicon dioxide, is formed of a transparent mixture with long-term stability to the precipitation of a solid phase even in the case when the heating phase of oxide, hydroxide or carbonate presents a dispersed solid material in the form of particles large enough they can be easily dissipated and the mixture prior to heating was muddy. Prepared by heating a mixture can be mixed with either water-soluble and/or dispersible in water by polymers, which are polyoxyalkylene polymers and/or copolymers of n-vinylphenol or water-soluble hexavalent and/or trivalent chromium with obtaining a composition which improves the corrosion resistance of metals treated with this composition, particularly after subsequent painting. 3 S. and 18 C.p. f-crystals, 8 PL.

The present invention relates to a method for surface treatment of metals aqueous acidic compositions for improving the corrosion resistance of the treated metallicheskaya protective layer on an organic basis. The main purpose of the present invention is to provide persistent storage, odnoupakovochnye means for processing, which can be practically free from hexavalent chromium, but almost able to protect metals similar means known in the art for processing, containing hexavalent chromium, or which can increase the stability of the processing solutions containing hexavalent chromium.

In modern technique known to a very wide variety of materials in common with the same purpose as the present invention, but most of them include hexavalent chromium or other inorganic oxidizing agents which are environmentally undesirable. Below are the specific technical solutions that, in the opinion of the applicant, being the closest to the present invention.

In the description to the us patent 5089064, issued on February 18, 1992 in the name of the Region (Reghi), proposes a method of processing aluminum composition, which includes forcerenew acid (H2ZnF6), water soluble or dispersible polymer of 3-[N-alkyl(C1- C4)-N-2-acetylaminophenol]-4-oxysterol and dispergirovannoyj dioxide to kremniya means for processing peculiar to the slow sedimentation of dispersed kremmidiotis component. In practice, this means that for best results, at least two components, one of which includes silicon dioxide, and the other it does not contain, should be stored separately and mixed just prior to use.

In the description to the us patent 4963596, issued October 16, 1990 , in the name of the overall forest, and others, refers to the processing of metals using water-soluble derivatives of polyvinylene, including here, in addition to numerous other options, combinations of these polymeric materials with dispersed silicon dioxide.

In the description to the us patent 4921552, issued may 1, 1990 in the name of sander and others, we are talking about handling aluminum composition, which contains forcerenew acid, hydrofluoric acid and water-soluble polymer.

In the description to the application for the European patent 0273698 (published July 6, 1988) presents aqueous acid solutions for processing, which include compounds of trivalent metals, silica, and preferably Nickel and/or fluoride ions. Oppositely charged ions relative to these cations of trivalent metals, anions, can serve credift the planned processing of metal surfaces songs, which includes a water-soluble salt of zirconium and/or titanium, ether phosphoric acid and Inositol, and silicon dioxide. This composition may also contain organic binder such as polyvinyl alcohol.

In the description to the us patent 4277292, issued July 7, 1982 in the name of Tupper proposed treatment of aluminum surfaces in aqueous acidic composition comprising zirconium, fluoride and vegetable tannin.

In the description to the us patent 3506499, issued April 14, 1970 in the name of Okada and others, we are talking about the treatment of aluminum and zinc surfaces in an aqueous solution of chromic acid and colloidal silicon dioxide.

In accordance with summary of work C. M. Thomsen "High-Silica Fluosilic Acids Specific Reactions and the Equilibrium with Silica", Jour. Amer. Chem. Soc. , 74, 1690 - 93 (1952) refers to the possibility of obtaining highly concentrated on silica forcerenew acids with any desired redundant content of silicon dioxide, up to 18% excess in comparison with the composition, which is expressed by the formula H2SiF6by dissolving the hydrated silica in hydrofluoric acid. Forceremove acid with a high content of carbon dioxide credit the Oia hypothetical chemical reaction 4H++ 5 SiF6-2+ SiO2= 3 (SiE6- SiF)4-2+ 2H2O

approximately 100 to 10000.

In the description of a broad aspect of the present invention in all cases, except for the claims of the invention and working examples, as well as specifically stated otherwise, all quantitative numeric values that indicate the amount of materials or conditions of reaction and/or application, should be understood as modified by the word "about". Thus, as a rule practically preferred are values within the specific limits.

It was found that aqueous compositions that include (A) a component of dissolved fluorine-containing acids of one or more metals or metalloids elements selected from the element class, which includes titanium, zirconium, hafnium, boron, silicon, germanium and tin, and (B) component is one or more (i) dissolved or dispersed forms of metals and metalloids elements selected from the element class, which includes titanium, zirconium, hafnium, boron, aluminum, silicon, germanium and tin, and (ii) oxides, of hydroxides and carbonates of these metals, metallo who should be subjected to conversion in the aqueous composition, with long-term stability to spontaneous delamination or loss of sediment even in the case when a metal and/or metallogenia elements, oxides, hydroxides and/or carbonates, which are part of such compositions are in the form of dispersed solid materials, which could precipitate within just a few days, if they did not participate ever in the response.

These compositions are prepared by mixing, then combine either (i) with soluble or dispersible in water, a polymer and/or copolymer of one or more X-/N-R1-N-R2-aminomethyl)-4-oxysterols, in which x = 2, 4, 5 or 6, R1denotes an alkyl group containing from 1 to 4 carbon atoms, preferably a methyl group, and R2denotes the replacement group, which satisfies the General formula H (CHOH) -, where n is an integer from 3 to 8, preferably from 4 to 6, or (ii) with a composition containing hexavalent chromium and, optionally, but preferably, trivalent chromium. The prepared composition is acceptable for treatment of metallic surfaces to achieve excellent corrosion resistance, in particular after application of the normal protective is Ali, galvanized iron and steel, zinc and those alloys that include at least 50 at.% zinc, and, more preferably, aluminum and its alloys that contain at least 50 at.% aluminum. This treatment may consist of either coating liquid metal film of the composition, followed by drying this liquid film at the place of deposition on the metal surface, or by a simple introduction of the metal in contact with the composition for a period of time sufficient to impart increased resistance of the surface to corrosion, followed by rinsing before drying. Such contact can be achieved by spraying, dipping and using similar techniques, which themselves are known in the art.

It must be borne in mind that this description does not exclude the possibility is not specifically mentioned chemical interactions between these components, and illustrates instead the components of the composition in accordance with the present invention in the form in which they are commonly used as ingredients for the preparation of such compositions.

The extent to which its solubility is sufficient, fluorine-containing acid to the tuleniy method in accordance with one alternative embodiment of the present invention, you can freely choose from a class that covers H2TiF6H2ZrF6H2HfF6H2SiF6H2GeF6H2SnF6and HBF4and their mixtures, H2TiF6H2ZrF6H2HfF6,

H2SiF6, HBF4and their mixtures are preferred: H2TiF6H2ZrF6H2SiF6and mixtures thereof more preferred, and H2TiF6the most preferred. The preferred concentration of fluorine-containing acid component during the reaction is in the range from 0.01 to 7 mol/l (hereinafter "M"), more preferred from 0.1 to 6 M

Component (hereinafter sometimes referred to as "(B)") metal and/or metalloids elements and/or their oxides, hydroxides and/or carbonates are preferred from a class which includes oxides, hydroxides and/or carbonates of silicon, zirconium and/or aluminum, more preferably silicon dioxide. When implementing the method in accordance with one alternative embodiment of the present invention, a component can be used in any form in which it is quite concordantly that it can be easily dispersing predpochtitelnei to use such an integral part in amorphous form, than in the crystal, as for the preparation of compositions, which later turns out to be insensitive to the bundle, crystalline materials may require a significantly longer period of heating and/or higher temperature. You can use the solutions and/or sols, in particular silicic acid sols, but rather it is preferable that they were practically free of alkali metal ions, as set out below. However, in General it is most preferable to use a dispersion of silicon dioxide, prepared during the pyrogenic processes.

In this detailed description of the equivalent metal or metalloidal element or its oxide, hydroxide or carbonate is defined as the amount of material containing the total number of metal atoms and/or metalloids elements of the class, which includes titanium, zirconium, hafnium, boron, aluminum, silicon, germanium and tin, is equal to Avogadro's number (i.e 6,021023). The preferred ratio between the number of moles percolator component (A) and the total number of equivalents of component (B) in the aqueous composition is heated in accordance with one alternative embodiment of the present is about 1.5 : 1 to 5.0 : 1.0 in. If desired, component this component can be processed on its surface celanova agent combinations, or the like, which makes it surface refernet.

In accordance with one alternative embodiment of the present invention an aqueous composition comprising, preferably consisting essentially of, or more preferably consists of water and percolating component and ingredient of oxide (oxides), hydroxide (hydroxide and/or carbonate (carbonate) metal (metal) and/or metalloidal (metalloids) element (elements), as indicated above, is stirred for a period of time sufficient for the preparation of compositions, which is free from any noticeable stratification in the storage process during a period of 100 hours or more, preferably 1000 hours In the mixing process, the preferred temperature is in the range from 25 to 100oC, more preferably in the range from 30 to 80oC, and the period of time during which the composition is maintained at this temperature is in the range from 3 to 480 min, preferably from 5 to 90 min, and still more preferably from 10 to 30 minutes Usually for conversion COMEST, is not subjected to any surface treatment to reduce their hydrophilicity, it is better the shorter the duration of mixing and reduced temperature within the specified ranges, although in the case when the component (B) includes dispersed solid crystalline materials and/or solids, the surface of which is treated to reduce their hydrophilicity, will likely be required a greater duration and/or higher temperature at specified intervals. In particularly difficult cases, the presence of equipment to create pressure over the reaction mixture, the process can be carried out in conditions of even higher temperatures than the 100oC.

Regardless of the other parameters in the preferred embodiment, to maintain the above temperature range, the pH value of the composition, which combine components (A) and (B) above, should be maintained in the range of from 0 to 4, more preferably in the range from 0.0 to 2.0, or more preferably in the range from 0.0 to 1.0.

In a preferred embodiment, after exposure at a temperature above the temperature of the composition is brought to a level below the 30oC, and then it smesi is whether dispersible in water polyhydroxyalkanoate poly-p-oxysterol, as mentioned above and as further described in the U.S. patent 4963596 that for this reason, in full, if to exclude anything that contradicts any clear statement contained in this detailed description, referred to here as a reference, or (2) solutions of hexavalent chromium and, optionally, but preferably, trivalent chromium, as is in itself known in the technique of processing of metals, particularly aluminum and its alloys, with the aim of slowing down the process of corrosion. Acceptable and preferred polymers and methods of obtaining presented in detail in the description to the us patent 4963596. The preferred value of the weight ratio between the solid materials contained component (C) and the total amount of active ingredients of component (A) described above should be in the range from 0.1 to 3, more preferably from 0.2 to 2, or even more preferably from 0.20 to 1.6.

The composition prepared in accordance with the above method is another variant of the embodiment of the present invention. Usually preferred compositions in accordance with the present invention, which is defined above, is the art. So, exactly as described in the order of increasing preference, the preferred minimum number of each of the following components, regardless of other such compositions, when they are in direct contact with the metal in the implementation of the method in accordance with the present invention should contain no more than 1,0, 0,35, 0,10, 0,08, 0,04, 0,02, 0,01 or 0.001 wt.% each of the following ingredients: hexavalent chromium, ferricyanide, ferrocyanide, anions containing molybdenum or tungsten, nitrates and other oxidizing agents (and the content of such other compounds identified in accordance with their oxidation stoichiometric equivalent as nitrate), phosphorus - and sulfur-containing anions that are not oxidizing agents, cations of alkali metals and ammonium, and organic compounds with two or more hydroxyl groups per molecule and a molecular weight less than 300. Preferred minimum amounts of cations of alkali metals and ammonium applies only in respect of the compositions used in the implementation of methods in accordance with the present invention, which include the stage of drying place obrabatyvayutsya, which contains components (A), (B) and (C), as described above, when the composition in accordance with the present invention is introduced into contact with the metal surface, followed by washing this metal surface with water before drying, everyone ions of alkali metals and ammonium are usually removed by washing to the extent sufficient to avoid any significant diminution of protective abilities applied in the further protective coatings containing organic binder. In addition, the preference to minimize the amount of hexavalent chromium present due to the polluting effect of hexavalent chromium, and in cases where there are no legal restrictions against environmental pollution, and/or there are quite economical means of waste disposal with hexavalent chromium, not having harm to the environment, this preference becomes unusable. Indeed, in accordance with one of the special variants of the embodiment of the present invention, as already noted above, hexavalent chromium can be used to further improve the corrosion cm present invention proposes a method of processing metal composition, prepared according to the above. One variant of the embodiment of the present invention on the surface of the metal, it is preferable to apply the acidic aqueous composition, as mentioned above, with subsequent drying at the place of application. So, for example, metal coating liquid film can be performed by dipping the surface into a container with a liquid composition, by spraying on the surface of this composition, applying the coating to the surface by passing between the upper and lower rollers, the lower roller which is immersed in the container with the liquid composition, and the like, or by combinations of these methods. Excess liquid compositions which otherwise could remain on the surface before drying, can be removed before drying by any conventional method, in particular due to runoff under its own weight, with a rubber layer, passing between the rollers, and the like.

In that case, if the coating applied to the surface of a flat sheet or roll and apply techniques precisely controlled coating, in particular a device for coating corrugated roller, for direct coating can effective the surface. On the other hand, if the equipment for coating does not ensure simple accurate control of the coating with a small added amount of liquid to be equally effective to use a more dilute acidic aqueous composition with the application of a thicker layer of liquid coating, which contains approximately the same number of active components. In any case, the total number of items selected from a class which includes titanium, zirconium, boron, silicon, germanium, tin, contained in the coating material, which is dried by the application site on the workpiece surface, is in the range from 1 to 300, preferably from 5 to 150, more preferably from 5 to 100, mg/sq m of the surface.

Drying can be performed by any convenient method, many of which are in themselves known in the art; examples include drying with hot air and infrared radiation. Independently, it is preferable that the maximum temperature of the metal, which is achieved in the process of drying was in the range of from 30 to 200, preferably from 30 to 150, and even more preferably from 30 to 75oC. whether the 50 sec even more preferably from 2 to 10 seconds after completion of coating.

In accordance with another alternative embodiment of the present invention the treated metal is preferable to enter into contact with a composition prepared according to the above, at a temperature in the range from 25 to 90oC, preferably from 30 to 85oC, even more preferably from 30 to 60oC, during the period of time from 1 to 1800, more preferably from 1 to 300 seconds, more preferably from 3 to 30 seconds, after which the thus treated metal surface is washed with water in one or several stages, followed by drying. In this embodiment, at least the final rinse is preferable to use deionized, distilled or purified in any other way water. In addition, in this embodiment, it is preferable that the maximum temperature of the metal, resulting in the drying process, was in the range of from 30 to 200oC, preferably from 30 to 150oC, even more preferably from 30 to 75oC, and that no matter what the duration of drying was in the range of from 0.5 to 300 seconds, preferably from 2 to 50 seconds, in accordance with the present invention, salient features of which in the total above, it is possible and usually preferable to continue drawing on the dry metal surface, which is obtained by the above described processing, siccative coating or other protective coating, thicker in comparison with a coating, which is obtained in the earlier stages of the method of the present invention, which is described above, as this in itself is known in the art. It was established that covered so surface has excellent resistance to subsequent corrosion, as illustrated in the following examples. The class of protective coatings especially preferred type for use in conjunction with the present invention includes paints, enamels, varnishes acrylic and polyester-based, and the like.

In the process of the present invention, which includes other stages after treatment and education layer on the metal surface, as set forth above, and in accordance with that provided by the process in the environment in which the discharge of the waste hexavalent chromium or limited by law or difficult with Ekonomicheskiye surfaces with any composition, which includes in the following order of increasing preference more 1,0 0,35, 0,10, 0,08, 0,04, 0,02, 0,01, 0,003, 0,001 or 0.002 wt.% hexavalent chromium. However, in some special cases, hexavalent chromium may inform the treated metal surfaces significant additional protection against corrosion, which justifies the higher costs associated with the use of determined by the legislation of the containing waste.

Preferably processed in accordance with the present invention a metal surface is first cleaned of all contaminants, particularly organic contaminants and extraneous metal dust and/or inclusions. Such cleaning can be carried out according to methods which are in themselves known to any expert in the art and suitable for being processed metal material of a particular type. Thus, in particular, in the case of galvanized steel surfaces most preferably clear material conventional hot alkaline detergent solution followed by rinsing with hot water, removing excess moisture and drying. In the case of aluminum the surface most prepost is, then, optionally, to enter into contact in neutralizing acidic wash solution with subsequent introduction into contact with the aqueous acidic composition as set forth above.

The possibility of practical implementation of the present invention becomes even more clear from a consideration of the following non-limiting explanatory examples, and advantages of the present invention can be further assessed with reference to comparative examples.

Examples

Test methods and other General conditions

Test pieces of aluminum type 3105 was purified by spraying for 15 seconds at a temperature of 55oC water cleanser, which contained 28 g/l cleaning of the drug PARCO 305 (manufactured by industrial branch "Parker+Amchem division" company "Henkel Corp., Madison heights, Michigan, USA). After cleaning, the panels were washed with hot water, remove them with excess water and dried, followed by coating with a roller using acidic aqueous composition, which is described in each example and comparative examples below.

For the first group of examples and comparative examples below, those slow according to the present invention was dried by thermal (instant drying) in the infra-red furnace, in which achieved a peak metal temperature of approximately 49oC. the thus Treated samples were further coated in accordance with the recommendations of the suppliers of various technical paints, which further elaborated below.

T-test on bending (T-bend) was performed in accordance with the method D4145-83 American society for testing materials ("ASTM"); test for impact resistance (toughness) was performed in accordance with the method D2794-841E1 ASTM; test salt spray was carried out according to standard method B-117-90 ASTM; test spray salts of acetic acid was performed according to standard method B-287-74 ASTM standards and test humidity were conducted according to standard method D2247-8 ASTM. Tests on immersion in boiling water was carried out as follows: 2T-bend and shock reversible deformation was determined on the treated and painted panels. Then the panel was immersed for 10 min in boiling water under normal atmospheric pressure and studied plots panel, which mostly were subjected to a T-bend and shock reversible deformation, in order to determine the percentage of the paint film from the original kodali needleplate paint. Thus, the best possible score is 10, which indicates the absence of detachment: a rating of 5 indicates 50% delamination, etc.

Specific songs

Example 1.

5,6 weight.h. amorphous fume silica

396,2 weight.h. deionized water

56,6 weight.h. water 60% by weight fortechnology acid

325,4 weight.h. deionized water

to 216.2 weight. including an aqueous solution containing 10 wt.% solids, water-soluble polymer (adduct of manniche poly-4-vinylphenol N-methylglucamine and formaldehyde), obtained in accordance with the instructions in lines 39-52 column 11 description to the us patent 4963596.

Example 2.

58.8 weight.h. water 60% by weight fortechnology acid

646,0 weight.h. demonizirovannyj water

5.9 weight.h. amorphous fume silica

10.5 weight.h. hydroxide of zirconium

much as 278.8 weight.h. 10% by weight solution of the water-soluble polymer used in example 1.

Example 3.

62,9 weight.h. water 60% by weight fortechnology acid

330,5 weight.h. deionized water

6.2 weight.h. amorphous fume silica

358,9 weight.h. deionized water

241,5 weight.h. 10% in the. water 60% by weight fortechnology acid

2.1 weight.h. product Aerosil R-972 (surface treated dispersed silicon dioxide)

of 56.4 weight.h. deionized water

667,0 weight.h. deionized water

218,1 weight.h. 10% by weight of water-soluble polymer used in example 1.

Example 5.

58.8 weight.h. water 60% by weight fortechnology acid

3.7 weight.h. amorphous fume silica

10,3 weight.h. the basic zirconium carbonate

647,7 weight.h. deionized water

279,5 weight.h. 10% by weight of water-soluble polymer used in example 1.

Example 6.

52,0 weight.h. water 60% by weight fortechnology acid

297,2 weight.h. deionized water

3.3 weight.h. amorphous fume silica

9.1 weight.h. the basic zirconium carbonate

273,6 weight.h. deionized water

and 364.8 weight.h. 10% by weight of water-soluble polymer used in example 1.

Example 7.

11,0 weight.h. fume amorphous silica

241,0 weight.h. deionized water

114,2 weight.h. water 60% by weight fortechnology acid

633,8 weight. including water compositions prepared from the following components:< the experiments of examples 1-6 in the order listed components were loaded into the container, equipped with a mixer (glass containers are sensitive to chemical compositions, so they should not be used even in laboratory conditions, it was found that satisfactory are the containers of austenitic stainless steel type steel type 316, and the container is made of or fully lined with racks of plastics, in particular polymers of tetrafluoroethylene or of chlorotrifluorethylene). During each experiment, except for the experiment of example 4, after adding the silicon-dioxide component and to the subsequent addition of the above components, the mixture was heated to a temperature within 38-43oC and kept in this temperature interval within a time span of 20-30 minutes the mixture is Then cooled to a temperature below 30oC and without additional heating was mixed with the remaining components, continuing the stirring after the introduction of each component until a clear solution is formed.

During the experiment of example 4 as silicon dioxide is used the material with the surface of the particles, the modified silane, and due to its hydrophobic nature to achieve transparency of the mixture, which on the and process were the same, as in experiment example 1.

During the experiment of example 7, the first three listed component mixed among themselves and kept at a temperature of 40 5oC for 10 min with stirring, and then cooled. In a separate container, chromium trioxide CrO3dissolved in water, the weight, the number of which is approximately 15 times its own weight of the oxide, and this solution was added a slurry of corn starch in water, the weight amount which is 24 times more than its own weight. Then this mixture has stood for 90 min with careful stirring at a temperature of 88 6oC to restore some contained hexavalent chromium to trivalent chromium. Finally, this mixture was cooled with stirring and then added in a pre-cooked pre-heated mixture fortechnology acid with silicon dioxide and water. This song is used in a way that is well known in the art for compositions comprising hexavalent and trivalent chromium and dispergirovannoyj silicon dioxide, but it is much more stable in storage, without phase separation.

Comparative example 1

18,9 weight. including water 60% is eriment example 1.

617,5 weight.h. deionized water.

Comparative example 2

18,9 weight. including water 60% by weight fortechnology acid 71,8 weight.h. 10% by weight of water-soluble polymer that was used in experiment example 1.

909,3 weight.h. deionized water.

In the experiments of comparative examples 1 and 2 components are added in the order specified, with simultaneous stirring without heating before use in the processing of metal surfaces.

Input mass, specific of paint used and the results achieved with the use of some of the songs listed above, are presented in the following table. 1-5.

The storage stability of the compositions prepared in accordance with all the above examples, except for example 2, was so good that no phase separation after at least 1500 hours of storage was observed. With regard to example 2, after 150 h was set to precipitation of the low number of obvious a solid phase.

To obtain the results listed in the tables below, sushestvovanie another aluminum alloy. So, specifically, test pieces of aluminum type 5352 or 5182 was purified by spraying for 10 seconds at a temperature of 55oC water purified product, which consisted of 24 g/l cleaning of the drug PARCO 305 (manufactured by industrial branch "Parker+Amchem" company "Henkel Corp., Madison heights, Michigan, USA). After cleaning, the panels were washed with hot water, then they were sprayed with appropriate solutions for processing in accordance with the present invention, which were similar to those already described above in the examples of the same numbers, except that they additionally diluted with water to the concentration listed in the following tables, for 5 seconds, then washed with water and dried before painting.

In column OT Bend" in the following tables presents the results of the test procedure, which was carried out as follows:

1. Test O-T bend in accordance with the method D4145-83 ASTM.

2. One piece of tape Scotch # 610 firmly attach on the part of the panel by bending O-T and the adjacent flat area.

3. Slow retraction of the tape from bending and adjacent flat area.

4. Stage 2 and 3 is repeated using a new piece of tape at kardiashian from bending O-T to the flat area, with which, according to the observations, removed paint, evaluated according to the following scale:

Loss of paint in mm - Score scale

0 - 5,0

0,8 - 4,5

1,6 - 4,0

2,4 - 3,5

3,2 - 3,0

4,0 - 2,5

4,8 - 2,0

5,6 - 1,5

6,4 - 1,0

7,2 - 0,5

>7,2 - 0

In column "a 90-minute treatment with water vapor" in the tables below presents the results of tests that were conducted as follows.

1. Painted samples treated with water vapor through their exposure in the cooking pressure vessel or autoclave at the temperature of the water vapor 120oC for 90 minutes

2. The dyed sample is subjected to cross-cut two perpendicular incision; use the tool Gardner for cross-cuts with 11 knife blades, separated from each other by 1.5 mm

3. On cross-cut section is firmly fixed tape ScotohTM# 610.

4. Visiting subjected to cross-cut site for the evaluation of the paint that was not removed by the tape, and the state evaluate the number of which corresponds to one tenth of the percentage of the remaining paint.

5. Using a microscope with 10-80-fold increase visual is the density of the bubbles.

In column 15-minutes boiling with immersion in DOWFAXTM2A1" in the tables below presents the results of tests carried out after the following processing.

1. Prepare 1% by volume of a solution of the product DOWFAXTM2A1 in deionized water and brought to a boil.

2. Painted test panels immersed in the boiling solution prepared in stage 1, and soak in it for 15 min, after which the panel is removed, washed with water and dried.

Product DOWFAXTM2A1 is produced industrially by the company "Dow chemical", which it describes as 45% of the active dodecyltrimethoxysilane sodium. After this treatment the test with "cross-cuts" was similar to the above for stages 2-4 after a 90-minute treatment with water vapor". Test "shock reversible deformation conducted according to ASTM D2794 - 84E1 (for striking 20 inch pounds (in., 20 x 25.4 mm x 0,453 kg), after which the procedure was performed similarly to the above for stages 3-4 after a 90-minute treatment with water vapor". Test "swelling" was carried out as follows. Using a conventional knife from the back side of the test panel engrave slightly curved tape "V"about on hand for testing. The sample is placed in a vise and pliers to pull from a bent section with a constant slow movement. The part of the panel, which is located between the upper edges in close proximity to the top, and a line parallel to the top edge, but remote from it by 19 mm neglected. For the remainder of the panel measure the boundary peeling in millimeters. Most of the obtained values is fixed.

The results of tests conducted in accordance with these procedures, are summarized in the following table. 6-8.

A method of obtaining a composition for metal surface treatment, comprising preparing a mixture by mixing the components with water, wherein the mixing is carried out in two stages, first mix with water fluoride compound or a mixture of fluorine-containing compounds selected from the group of H2TiF6H2ZrF6H2HfF6H2SiF6H2GeF6H2ShF6, HBF4and dissolved and/or dispersed component selected from the group Ti, Zr, Hf, Al, Si, Ge, Sn, B, and oxides, hydroxides, carbonates of these elements and any mixtures thereof at a temperature and time sufficient to prevent the 5oC, after which the resulting mixture is mixed with a component selected from the group consisting of water soluble and dispersible in water, polymers and copolymers X-(N-R1-N-R2-aminomethyl)-4-oxysterols, where X=2,3,5,6, R1is an alkyl group containing from 1 to 4 carbon atoms, R2- replacing the group with the General formula H(CHOH)nn-3-8, two or more mixtures thereof, and dissolved hexavalent chromium at a temperature and time sufficient to prevent phase separation in the preparation of the mixture, and the stability of the mixture during storage for at least 100 hours at 20 - 25oC.

2. The method according to p. 1, wherein preparing a mixture containing from 0.01 to 7.0 M fluorine-containing compounds or a mixture of fluorine-containing compounds selected from the group of H2TiF6H2ZrF6H2HfF6H2SiF6, HBF4with a molar ratio of fluorine-containing component to a component selected from the group Ti, Zr, Hf, Al, Si, Ge, Sn, B, and oxides, hydroxides, carbonates of these elements and any mixtures thereof, in the range from 1 : 1 to 50 : 1, maintain the mixture at 25 - 100oC for 3 to 480 min, the resulting mixture is mixed with a component that includes such General Caicedo them and a total weight of fluorine-containing component is in the range from 0.1 : 1 to 3 : 1.

3. The method according to p. 1, wherein preparing a mixture containing from 0.1 to 6.0, MD fluorine-containing compounds or a mixture of fluorine-containing compounds selected from the group of H2TiF6H2ZrF6H2SiF6with a molar ratio of fluorine-containing component to the total number of oxides, hydroxides and carbonates of Si, Zr, Al in the range from 1.5 :1.0 to milking 20 : 1, and the pH value in the range from 0 to 4, maintain the mixture at 30 - 80oC for 5 to 90 min, the resulting mixture is mixed with component comprising such total amount of water-soluble and diperkirakan in water of the polymers and copolymers in which the weight ratio between them and the General weight of fluorine-containing component is in the range of 0.2 : 1 to 2.0 : 1.

4. The method according to p. 3, characterized in that the first, cook the mixture with a molar ratio from 1.5 : 1 to 5 : 1 and a pH in the range of 0 to 2, the mixture is maintained at 30 - 80oC for 10 - 30 min, the resulting mixture is mixed with water-soluble and dispersible in water, the polymers and copolymers and copolymers with a weight ratio of them, and fluorine-containing component in the range of 0.2 : 1 to 1.6 : 1.

5. The method according to p. 1, wherein preparing the mixture, containing the equivalents of silicon dioxide in the range from 1.5 : 1.0 to 5 : 1 and pH 0 - 1,0, maintain the mixture at 30 - 80oC for 10 - 30 min, the resulting mixture is mixed with component comprising such total amount of water-soluble and dispersible in water, polymers and copolymers of X-{ [(N-methylamino)glucamine] methyl} -4-oxysterols, where X=2,3,5,6, in which the weight ratio between them and H2TiF6is in the range from 0.20 : 1 to 1.6 : 1.

6. The method of metal surface treatment, wherein the treatment is carried out by coating the metal surface with a layer of the composition obtained under item 1, the thickness at which the layer contains elements selected from the group Ti, Zr, B, Si, Ge, Sn, the total number of from 1 to 300 mg/m2metal surface, and drying the layer in place without intermediate rinsing.

7. The method according to p. 6, characterized in that the coating of metal surfaces is performed by the layer composition thickness at which the total number of elements in the layer is from 5 to 100 mg/m2metal surface, and drying is carried out in the next 2 to 50 C.

8. The method according to p. 6, wherein the treatment is carried out with a composition obtained by p. 2.

9. The method according to p. 6, characterized in that the processing performed by the composition p is obtained on p. 4, when the thickness of the layer, the total number of items which ranges from 5 to 150 mg/m2metal surface.

11. The method according to p. 6, wherein the treatment is carried out with a layer of a composition obtained by p. 4, when the thickness of the layer, the total number of items which ranges from 5 to 100 mg/m2metal surface, and drying is carried out in the next 2 to 50 C.

12. The method according to p. 6, characterized in that the metal surface is covered with a layer of liquid composition obtained under item 5, when the thickness of the layer, the number of cells which is from 5 to 150 mg/m2metal surface.

13. The method according to p. 6, characterized in that the metal surface treatment is performed by the layer of the composition obtained under item 5, when the thickness of the layer in which the total number of elements is 5 to 100 mg/m2metal surface, and the drying is conducted for 2 to 10 s, with a maximum metal temperature of 30 - 75oC.

14. The method of processing a metal surface, wherein the treatment is carried out by introducing a metal surface in contact with the liquid composition obtained by p. 1, at 25 - 90oC for 1 - 1800, removal of the surface of eskay surface with a liquid composition is carried out at 30 - 60oC for 3 to 30 C, and the drying is conducted for 2 to 50 C.

16. The method according to p. 14 characterized in that the treatment is carried out with a composition obtained by p. 2.

17. The method according to p. 14, characterized in that the processing composition obtained under item 3.

18. The method according to p. 14, characterized in that the contact of the metal surface with a liquid composition obtained by p. 4, is carried out at 30 - 85oC for 1 to 300 C.

19. The method according to p. 14 characterized in that the contact of the metal surface with a liquid composition obtained by p. 4, is carried out at 30 - 60oC for 3 to 30 C, and the drying is conducted for 2 to 10 seconds

20 . The method according to p. 14, characterized in that exercise contact a metal surface with a liquid composition obtained by p. 5, at 30 - 85oC for 1 to 300 C.

21. The method according to p. 14, characterized in that exercise contact a metal surface with a liquid composition obtained by p. 5, at 30 - 60oC for 3 to 30 C, and the drying is conducted for 2 to 10 s at maximum metal temperature 30 - 75oC.

 

Same patents:

FIELD: coating of metal articles, in particular corrosion-resistant chemical conversion coatings.

SUBSTANCE: coating of structural alloys, preferably aluminum and aluminum-based alloys is carried out by treatment in acid aqueous solution containing water soluble chromium(III) compounds, fluoride, and corrosion strength improving additive (preferably nitrotris(methylene)triphosphonic acid. Claimed method includes treatment of metal substrate with said solution free from hexavalent chromium. Article contains metal substrate, coated as described above. Article may also contain anodized aluminum substrate with sealed coat comprising trivalent chromium and phosphorus applied on anodized coat.

EFFECT: trivalent chromium-based chemical conversion coating free from hexavalent chromium; effective stable coating solution.

23 cl, 8 dwg, 2 tbl, 1 ex

FIELD: mechanical engineering; production of foil from beryllium.

SUBSTANCE: proposed method consists in placing the beryllium blank into metal casing, sealing-up, rolling at temperature of 600-800°C and removal of casing. Prior to placing the blank into casing, it is placed into solution for passivation and is heated in air at temperature of 550-600°C during period sufficient for forming modified passive film up to 10 mcm in thickness; passivation solution contains the following components, g/l: potassium bichromate, 150-200; hydrofluoric acid, 9.5-9.8; sodium fluoride, 5-10; beryllium, 0.2-0.4; water, up to 1 l. Proposed method excludes fusion of beryllium blank with metal of casing in rolling and contamination of beryllium with alloying elements of metal of casing.

EFFECT: enhanced mechanical properties of foil; increased vacuum density at retained radiation transparence.

3 cl, 3 tbl, 1 ex

FIELD: process for coating of parts made from aluminum of alloys thereof.

SUBSTANCE: method involves preparing part surface for coating process; dipping part into solution of composition including, g/l: orthophophoric acid 40-50, chromic anhydride 5-7, hydrofluoric sodium 3-4, at temperature of 20-30 C; holding in solution during 4-7 min; washing with cold running water and drying. Parts dipped into solution are subjected to harmonic vibrations with fixed frequency ranging between 300 Hz and 600 Hz and mean-square acceleration of 9-11 m/s.

EFFECT: provision for producing of thick corrosion-resistant coating on parts made from aluminum and alloys thereof.

3 ex

FIELD: chemistry.

SUBSTANCE: method of conditioning of surface of aluminium and its alloys for soldering which includes treatment of the surface with degreasing and etching solutions followed by treatment in water solution of hydrofluoric acid mixed with fluoride of an alkaline metal with the following concentration of ingredients in solution, % w/w: hydrofluoric acid - 1-27, fluoride of an alkaline metal - 1-50, water - the rest of solution.

EFFECT: high quality of aluminium and its alloys soldering is ensured.

3 cl, 4 tbl

FIELD: technological processes.

SUBSTANCE: invention may be used in radio engineering industry, instrument making, aircraft industry for preparation of pore-free thick coatings on parts made of aluminium and its alloys. Method includes preparation of their surface for coating, immersion into solution with the following composition, g/l: orthophosphoric acid 40-50, chrome anhydride 5-7, hydrofluoric sodium 3-4, at temperature of 20-30°C, soaking in solution for 4-7 min, flushing in clod running water and drying, at that parts that are immersed into solution are exposed to wideband accidental vibration in the range of 10-1000 Hz and mean-square acceleration of 18-22 m/sec2.

EFFECT: development of method for application of conversion coating on parts made of aluminium.

3 ex

FIELD: welding jobs.

SUBSTANCE: invention can be used in soldering silumin coated aluminium and aluminium alloys at high temperatures. The proposed method comprises the steps that follow. First the surface to be soldered is degreased and/or degreased and etched. Then the said surface is subjected to treatment by water solution of fluorohydrogen acid mixed with alkaline metal fluorides, the concentration of components in the solution making, in percent by weight, the following values, i.e. fluorohydrogen acid - 1.0 to 35.0, alkaline metal fluoride - 0.2 to 22.0, water - the balance. Now the surface is dried and soldered in inert gas atmosphere with no fluxes, irrespective of curing time after treatment.

EFFECT: layer of aluminates produced on soldered surface boats practically equal thickness and provides for high quality of soldering.

4 cl, 1 tbl, 8 ex

Coating composition // 2363769

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for coating base metals, to coating obtained from the said compositions, as well as to the method of obtaining the said compositions. The coating composition contains an aqueous mixture, containing particles, stable towards acids, and one or several fluoro-acids, where content of particles stable towards acids ranges from 0.005 to 8 wt % in terms of dry mass. The base metal coating contains particles, stable towards acids, attached to the base by a metal oxide matrix. Specific density of the base metal coating ranges from 5 to 50 mg/ ft2 (53.82 - 538.2 mg/m2). The method of producing the composition involves production of particles stable towards acids and one or several fluoro-acids, mixture of the said particles stable towards acids and one or several fluoro-acids in water, where pH of the coating composition ranges from 2 to 7, and content of particles stable towards acids in the coating composition ranges from 0.005 to 8 wt % in terms of dry mass.

EFFECT: invention allows for production of coating compositions, which significantly reduce the level corrosion of objects, containing several base metals.

40 cl, 3 dwg, 7 tbl, 20 ex

FIELD: metallurgy.

SUBSTANCE: coating method of metal surface or metal alloy surface involves contact of the above surface with effective amount of water treating solution or dispersion, which is free from chromate and (a) material or materials containing one or several elements chosen from elements of group IVB, (b) fluoride, (c) phosphonic acid or phosphonate, where the above phosphonic acid or phosphonate is chosen from the group containing compounds with the above formulae II, III or IV. Acid water composition or dispersion for forming of converting or passivating coating on metal surfaces is free from chromate and contains material or materials containing one or several elements chosen from elements of group IVB, (b) fluoride, (c) phosphonic acid or phosphonate, where the above phosphonic acid or phosphonate is chosen from the group containing compounds with the above formulae II, III or IV.

EFFECT: improving adhesion of coatings and corrosion protection.

19 cl, 5 tbl, 5 ex

FIELD: metallurgy.

SUBSTANCE: 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.

EFFECT: increased corrosion resistance of metal surface of composition meeting ecological requirements.

19 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: 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.

EFFECT: invention enables to obtain a coating with good adhesion strength with a metal surface and high corrosion resistance made from an aqueous composition which meets environmental requirements.

27 cl, 1 tbl

FIELD: metallurgy.

SUBSTANCE: invention refers to machine building and to process of fabricating items out of non-ferrous alloys, particularly to protective coatings against gas corrosion during continuous operation and at process heating during production of items and semi-products of high quality out of beryllium and its alloys at thermal and thermal-mechanical forming operations. The method includes preparing surface of the item and its successive immunisation by means of applying water solution on the surface of the item; this water solution contains potassium bichromate 170-250 g/l, hydrofluoric acid 7.5-11.5 g/l, sodium fluoride 3-12 g/l, beryllium 0.1-0.5 g/l, and chromium oxide 0.1-0.5 g/l with following thermal treatment of this surface and with applying on it a non-organic enamel coat of the system B2O3-PbO-CaO-MgO-Al2O3-Cr2O3-CoO-SiO2. Immunisation is carried out during 30-80 minutes at the temperature of 45-70°C, while thermal treatment of the immunised surface is performed at the temperature of 550-650°C during 0.5-1.5 h. Forming non-organic enamel coating of system B2O3-PbO-CaO-MgO-Al2O3-Cr2O3-CoO-SiO2 is executed at the temperature of 520-600°C during 0.1-0.5 h.

EFFECT: producing protective coating possessing upgraded temperature resistance up to 1200°C and high heat resistance on items from beryllium and its alloy.

4 cl, 3 tbl

FIELD: metallurgy.

SUBSTANCE: solution of oxidation of aluminium alloys includes components at the following ratio, g/l: chromic anhydride 4.0 - 7.0, orthophosphoric acid 40.0 - 50.0, sodium fluoride 5.0 - 7.0, 6-hydrous zinc nitrate 4-5.

EFFECT: invention allows obtaining on aluminium and its alloys the quality coating, solid oxide file uniform as to thickness and withstand the action of cyclic change of temperature and tropic humidity during 12 days.

3 ex

FIELD: metallurgy.

SUBSTANCE: method includes degreasing of products in gasoline, drying in air at the room temperature, alkaline processing in the solution containing 400-450 g/l of sodium hydroxide at the temperature 100-120C, washing with warm and cold flowing water, processing in the solution containing 100-150 g/l of chromic anhydride at the temperature 15-30C, washing in the trapping bathtub with the distilled cold water, washing with flowing cold water and application of chemical oxide coating in the solution containing, g/l: chrome anhydride - 4.0-8.0, fluoric sour ammonium - 1.5-2.0, ferricyanic potassium - 0.5-1.0, at the temperature 15-30C within 10-20 minutes. Thickness of the coating layer is 0.5-5.0 mcm.

EFFECT: making a conducting coating stable to corrosion and with uniform thickness along the whole surface of the processed product.

2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: solution contains components in the following ratio, g/l: sodium bichromate 45.0-48.0, sulphuric acid 55.0-60.0, nitric acid 390.0-400.0, compounds containing fluoride ions 55.0-60.0, compounds containing ammonium ions with respect to the pure substance 40.0-50.0, cobalt sulphate 1.0-5.0.

EFFECT: invention provides high adhesion and ornamentality of the coating, moisture resistance, corrosion resistance, high manufacturability, capacity to recreate a passive film in case of mechanical damage to the coating.

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