The copper deposition method disproportionation without ammonia

 

(57) Abstract:

For deposition of metallic copper on a catalytically activated surface to ions of divalent copper in aqueous solution not containing added ammonia as a reducing agent for the formation of hydroxide monovalent copper without a significant recovery to elemental or metallic copper, then carry out the disproportionation of the resulting hydroxide monovalent copper with the purpose of deposition of metallic copper. Does not contain ammonia reducing agent is preferably hydroxylamine or its salts, (e) used in conjunction with water-soluble hydroxide of alkali or alkaline earth metal, preferably sodium hydroxide. 4 C. and 35 C.p. f-crystals, 1 table.

The scope of the invention

The present invention is directed to a method of deposition of copper, and in particular to an improved method and system for deposition of metallic copper on a catalytically activated surface by regulation disproportionation hydroxide monovalent copper.

Art

The deposition of copper by disproportionation disclosed in U.S. patent 3,963,842 (Sivertz and others) owned pravoprimenitelnoj in the manufacture of mirrors) or other catalytically activated surface by (1) rapid recovery complex tetraamine ions of divalent copper in aqueous solution to complex diamino ions monovalent copper in the absence of a significant recovery to metallic copper, and (2) subsequent implementation of a managed disproportionation received monovalent ions of copper, with the aim of deposition of metallic copper mainly on the surface. The initial stage of restoration carried out by applying a class of remedial agents selected from nitrogen compounds containing one or two nitrogen atom and having the formula

X-NH-Y,

where

X is hydrogen, hydroxyl, hydroxyl-substituted lower alkyl or benzosulfimide groups;

Y is NH2or NH2Z

If Y is NH2Z, then X is hydrogen, hydroxyl-substituted lower alkyl or benzosulfimide, and Z is an acid, or-H, or HZ. If Z is HZ, then X is hydroxyl. Open specific representatives were hydrazine, salts of hydrazine with sulfuric or acetic acid, monosubstituted hydrazine derivatives, including 2-hydroxyethylhydrazine and p-hydrazinobenzothiazole acid, hydroxylamine and hydroxylamine salt with sulfuric or acetic acid. Also been disclosed an auxiliary reducing agents (reductants), including symmetrically disubstituted hydrazines used together with members of hydrazine powered stimulants, such as di-2-hydroxyethylhydrazine, hydrazobenzene and hydrocarbonate, and other nitrogen compounds, for example, aminoguanidinium. The use of hydroxylamine sulphate preferably is of the oxidation States of Cu+2in the form of Cu+1you must use the ammonium hydroxide together with hydroxylamine sulphate. Then diamino-ions to monovalent copper disproportionate to metallic copper and divalent state when mixed with certain organic acid activators, such as hydroxycarboxylic acids, more preferably an alpha hydroxy acid such as glycolic, malic, tartaric, sugar, lemon and/or lactic acid and the like, dicarboxylic acids such as succinic acid and the like, and sulfamic acid. In another embodiment, used for the disproportionation activator-modifier may be chelating amine, such as Ethylenediamine, triethyltetramine, similar bonds alkylamines, or the activator-type inorganic acid, such as sulfuric or phosphoric acid, together with modifier specified organic acids, these chelating amines or combinations thereof. After the disproportionation of copper in the metallic state is deposited on glass, silver metal film or other activated surface.

A solution of ammonium copper (Cu+1) complex is also described in less successful method of deposition of copper by disproportianately above method (Sivertz and others), usually works well, is licensed and used in many factories producing mirrors around the world. However, some aspects of this process it is desirable to improve. Used in the above-mentioned method, the ammonia complex is copper (Cu+1in the air are destroyed within a few minutes, therefore it is usually necessary to obtain in a closed container. The only way to save copper (Cu+1) complex is to keep it under a layer of nitrogen or other means to isolate it from contact with oxygen, which is not always possible in practice. Applied the above method (Sivertz and other) metal film of copper also has a tendency to fade under the influence of water vapor, especially in the presence of volatile ammonia vapor from the process, which complicates protection when handling. Consider also that the reaction rate of this process is not controllable. In addition, manufacturers are always looking for reactions with high efficiency to save material costs and increase the speed of the process. Thus, there is a strong need for improvement of the method according to the specified patent (Sivertz and others).

Recent regulations in the U.S. and in some other place in the world autoout content in the environment in the workplace. Obeying these rules force companies to completely eliminate the use of ammonia in their processes or install expensive equipment that controls emissions to avoid the presence of ammonia in the outgoing stream and in the workplace. Conventional technology and the best available equipment that can be used to remove ammonia from upstream, expensive and not very effective. Distillation of air only moves the ammonia in the air and eliminates product contamination. Using chlorine, you can also achieve a decomposition of ammonia, but this system results in the formation of chlorinated organic compounds that are potential pollution and are hazardous to health. The preferred method also uses the activator-modifier hydroxycarboxylic acids such as citric acid, but requires the use of such organic acids in an amount that causes a significant need for chemical oxygen and biological oxygen into the flowing stream. The use of much smaller quantities of lemon or other organic acids could help to adjust the amount of undesirable reaction products from the point of the vision is th invention is the provision of an improved method for the deposition of copper, which excludes the application of ammonia and the attendant problems associated with the control and removal of process ammonia.

Another object of the present invention is to increase the efficiency of the above-described method (Sivertz and others) deposition of copper.

Another object of the present invention is the provision of a method of regulating the speed of reaction of the above-described method (Sivertz and others) deposition of copper.

Another object of the present invention is an improvement of the method of deposition of copper by reducing the amount of organic acid required for the disproportionation of ions of monovalent copper.

Another object of the present invention is the provision of a received non-electric (chemical) by the coating film of the deposited copper, which is not soon dims under the action of water vapor.

Another object of the present invention is to improve the above-described method of deposition of copper by eliminating the need for nitrogen surface layer over the complex Cu+1(application of nitrogen for isolation of a complex of monovalent copper) or in another case of this complex in novecentos copper for use in the above-described method, the deposition of copper, where you can get the solution of a complex of monovalent copper and is easy to contain or to be stored for a relatively long period of time before deposition of the copper film on the desired substrate by disproportionation.

Another object of the present invention is the provision of compositions for the implementation of the above purposes.

Description of the invention

The above and other objectives that are apparent to specialists, reach the present invention relates to a method for deposition of metallic copper on a catalytically activated surface by means of a quick recovery of ions of bivalent copper in aqueous solution ions to monovalent copper, which instantly transformed into insoluble hydroxide monovalent copper without a significant recovery to elemental or metallic copper and further effectively controlled disproportionation of the resulting hydroxide monovalent copper with the purpose of deposition of metallic copper mainly on this surface. In the first aspect, the method includes adding to the ions of divalent copper does not contain ammonia reductant for holding vosstanovlenie and its salts with water-soluble hydroxide of alkali or alkaline earth metal or other not containing ammonia alkaline compound, more preferably sodium hydroxide. In addition, the recovery of ions of bivalent copper exercise, adding to the solution antiaglomerate agent to control the dispersion of the hydroxide precipitate monovalent copper, preferably of high molecular weight alcohol, such as sorbose, fructose, dextrose or invert sugar. Antiaglomerate agent is present in amounts insufficient to affect the recovery of ions of bivalent copper separately.

The process of disproportionation hydroxide monovalent copper is carried out by adding an acid activator, which includes hydroxycarboxylic acid or its salt to cause precipitation of metallic copper mainly on a catalytically activated surface, the trigger hydroxycarboxylic acid is present in solution in an amount of not more than one (1) mole per mole of hydroxide monovalent copper. Preferably the activator-modifier hydroxycarboxylic acid or salt is citric acid, malic acid, tartaric acid or maleic acid, which additionally contains an inorganic acid, such as sulfuric acid. The activator can also add mo is Ernesto-active additives, which can slow irregular decomposition to useless muddy precipitate metallic copper than the desired deposition of copper.

In another aspect, the invention includes not containing ammonia system for the deposition of copper on a substrate, which comprises an aqueous solution containing ions of bivalent copper, an aqueous solution of reducing agent copper containing nitrogen, an aqueous solution of alkali or alkaline earth metal and an aqueous solution of an activator containing hydroxycarboxylic acid or its salt or inorganic acid in combination with a hydroxycarboxylic acid or salt. For recovery of ions of bivalent copper hydroxide to monovalent copper reductant solution of divalent copper preferably contains hydroxylamine and its salts, the alkaline hydroxide or alkaline earth metal or other alkaline compound that does not contain ammonia, preferably is sodium hydroxide. In addition, to save hydroxide monovalent copper, dispersed as fine particles, the system may contain antiaglomerate agent, preferably high molecular weight alcohol, more preferably, sorbose or invert sugar. Antiaglomerate agent is nteu copper. An aqueous solution of the activator preferably contains a hydroxycarboxylic acid or salt in an amount of not more than about 65 g/l, while the activator-modifier hydroxycarboxylic acid or salt preferably contains citric acid, malic acid or tartaric acid and further comprises an inorganic acid. The system can also include modifying the speed of the surface-active agent of the type indicated above.

Ways of carrying out the invention

The method of the present invention is an improvement of the above-described method of U.S. patent 3,963,842, the description of which is incorporated herein by reference. However, that the invention can be used for deposition of metallic copper on a variety of substrates or catalyzed surface, I believe that it is particularly useful in the manufacture of mirrors in the deposition of copper on the layer of silver on the glass or on the glass itself. First, you can increase the sensitivity of the surface of the glass (to make hypersensitive) by applying known methods of solution douglasthe tin, followed by the application of ammonium nitrate of silver. When copper is precipitated on the silver layer, you can apply any of the methods USA N 4,102,702 (Bahls) or U.S. patent N 4,192,686 (authors present invention). The preferred method of applying silver is a method disclosed in U.S. patent N 4,737,188 (Bahls). Immediately after deposition of a layer of copper over it put a protective resin or other coating, such as a resin that does not contain lead, disclosed in U.S. patent N 5,075,134 (Sanford) and U.S. patent N 5,094,881 (Sanford and others). Descriptions of all these above-mentioned patents are incorporated herein as references.

The system of the present invention may consist of three (3) or four (4) components. These components are present in the form of aqueous solutions, which during transportation and storage can be in a concentrated form before you can be diluted with deionized water to a working concentration.

The first component includes ions of bivalent copper, preferably from neamine complex salt of copper (Cu+2), such as sulfate or nitrate, more preferably in the form of the pentahydrate of copper sulfate (CuSO45H2O). The reductant solution of divalent copper to monovalent, which can be provided separately in the form of the second component, but it is more convenient to include in the first component contains a compound of nitrogen with optional auxiliary reducing agent, preferably one or more compounds, op is on. Other reducing agents may include hydrazine, aminoguanidinium, carbohydrate and dithionite or any other connection capable of restoring ions of divalent copper ions to monovalent state in the absence of ammonia. The concentration of nitrogen or a reducing agent can vary from about 25 to 65 g per liter, preferably at least about 45 g/l, the concentration should be sufficient to recover all ions of bivalent copper hydroxide to monovalent copper, as shown stoichiometric equation, when the reducing agent is hydroxylamine sulphate:

< / BR>
Recovery of ions of bivalent copper carried out by adding a third component, a water-soluble hydroxide of alkali or alkaline earth metal, preferably sodium hydroxide or potassium, or other not containing ammonia alkaline agent, such as sodium carbonate or potassium, to increase the alkalinity of the mixture of ions of bivalent copper and reductant in the stoichiometric ratio corresponding to the above reaction equation. Preferably a hydroxide of an alkaline or alkaline earth metal is sodium hydroxide. The reaction is fast clicks is that has the appearance of "orange slime". In addition, there is a gaseous nitrous oxide coming out of the reaction vessel in the form of bubbles.

To act as antiglomerular agent and conservation of particles, Cu(OH) from the formation of large flakes or lumps, the reductant solution of divalent copper added to the first component preferably includes, as an optional component, a polyhydric sugar or alcohol (polyol) such as dextrose, fructose, glucono-deltalactone, glucoheptonate sodium /L-sorbose, invert sugar, sucrose, D-galactono-gamma-lactone, 2-keto-D-gluconic acid, glycine, D-mannose, D-galactose and the like. The preferred polyols are sugar compounds, such as sorbose and invert sugar. When these compounds could theoretically be used for recovery of copper, the amount used in this case, the polyol is less than sufficient to restore the number of ions of bivalent copper to the monovalent state. The concentration of the polyol can be varied from about 1 to 200 g per liter per mole used salts of copper, but is preferred amount of about 10 to 100 g/l and most preferred about 65-75 g/l per mole of salt of copper. When there is no terragni bonds between molecules of the obtained hydroxide monovalent copper. Consider that the molecules of hydroxide monovalent copper formed during the initial recovery ions of divalent copper in the first component, tend to form hydrogen bonds with polyols (via hydroxyl group), but not with other molecules hydroxide monovalent copper, maintaining a high degree of dispersion of the hydroxide precipitate monovalent copper in the form of relatively small particles. Found that this ultimately depends on the application of a more uniform coating of metallic copper in the second stage (disproportionation).

As established earlier, the reducing agent can be provided in the form of a solution of the individual or of the second component that can be added to the first component of the solution of divalent copper immediately before the addition of the solution of the third component, preferably sodium hydroxide or potassium. Preferred the following order of addition: for the second component (reducing agent) should the third component (the hydroxide of alkali or alkaline earth metal). If the hydroxide of alkali or alkaline earth metal are added to a solution of divalent copper to reductant, the precipitate of the hydroxide of the divalent Lenten copper. In spite of the necessary suspension of hydroxide monovalent copper (orange sludge), the preferred ratio of the salt of copper (Cu2+), the reducing agent is hydroxylamine and hydroxide of alkali or alkaline earth metal are shown above the stoichiometric equation, the change in the number or reductant or hydroxide of alkali or alkaline earth metal in the direction of reduction of the stoichiometric amount will result in reduction of yield hydroxide monovalent copper. Similarly, the use of amounts greater than stoichiometric, is wasteful, but in both cases, the monovalent hydroxide copper get in the correct state.

Unlike patent '842 (Sivertz and others) receiving and storing suspension (slurry) hydroxide monovalent copper can be performed in open vessels and stored without using nitrogen gas for insulation from air and, if necessary, be stored for months, back in the divalent oxidation state does not occur. This feature allows the use of simple open tanks for all components and the resulting hydroxide monovalent copper, in contrast to the way '842 (Sivertz and others) does not require Dor and, obviously, you need to avoid certain anions other than hydroxyl groups, which give insoluble salts with monovalent ions of copper, as in the reagents, and in the form of impurities in the reagents. Especially among these anions should be mentioned chlorides, iodides, sulphides, cyanides and thiocyanates. This is not always possible in the production, and the admixture of sodium chloride in alkaline hydroxide or alkaline earth metal preferably should be less than 300 ppm (million shares). On the other hand it is shown that the carbonate that can be added or which is usually present in the hydroxide sodium carbonate sodium (Na2CO3), has a positive impact on the effectiveness of the coating, when present in an amount up to about 33 weight % of sodium hydroxide, although excessive amounts will cause unwanted stains from precipitated copper.

In order to control the coating of copper on a catalytically activated surface, a monovalent hydroxide of copper obtained from the combination of the first, second and third components, the hydroxide of monovalent copper to add a fourth component containing the activator is an organic acid. This chetvertyy hydroxycarboxylic acid, more preferably the alpha-hydroxy acid, such as malic acid, citric acid or tartaric acid. The activator can be modified by the addition of inorganic acids such as sulfuric, phosphoric or sulfamic acid, or an amine, such as Ethylenediamine, Triethylenetetramine or similar bonds alkylamines. Used here, the term "inorganic acid" includes partially neutralized forms of these acids, such as sodium bisulfate. The inorganic acid can be used without organic acid activator, but the result is less desirable chalky appearance of the deposited copper. It is preferable to apply the activator-modifier comprising sulfuric acid or citric acid, or malic acid, tartaric acid, or combinations thereof.

Alternatively, the hydroxycarboxylic acid can be included in the solution of salt of divalent copper (the first solution), which requires additives inorganic acid as activator-modifier (the fourth component). In this case, the hydroxycarboxylic acid can be added to the first component in the form of salts, namely, in the form of salts of alkali or alkaline earth metal. Hydroxycarboxylic acid or its salt may be added to luee to the fourth component in the form of acid. When the first component salt of hydroxycarboxylic acid may be, for example, in the form of citrate, tartrate or salt of malic acid.

The preferred concentration of the inorganic acid is a value in the range from about 40 to 100 ml/l, when the first component contains copper ions from 220 g/l CuSO45H2O. surprisingly, the organic acid or its salt can be used in smaller quantities than 200 g/l, as used in the patent '842 (Sivertz and others), and the preferred concentration is from about 40 to 120 g/l, preferably at least about 60 g/l, most preferably about 65 g/L. This corresponds to less than one pray organic acid or salt per mole of hydroxide monovalent copper, preferably less than half mole of organic acid or salt per mole of hydroxide monovalent copper. After the addition of acid activator pH of the entire solution falls below 7, preferably below 3. Consider that the oxide monovalent copper can be dissolved ions to monovalent copper, and probably complexesa with hydroxycarboxylic acid, thus, free ions of monovalent copper to be mobile for the reaction of disproportionation. For the reaction to occur is Bladet worst quality and efficiency below than when using the above combination of inorganic and organic acids.

The preferred system of the present invention includes the following preferred compounds in aqueous solutions (the number given for the concentrated form):

CU-275 (solution of copper)

275 g/l of pentahydrate copper sulphate

CU-1C (solution of reducing agent)

184 g/l of hydroxylamine sulphate

66 g/l L-sorbose

CU-100 (solution of copper + reductant)

4 part of the CU-275

1 part CU-1C

CU-200 (solution of an alkali metal)

380 g/l of sodium hydroxide

CU-300 (activator solution)

65 g/l citric, malic, or tartaric acid

80 ml/l of sulfuric acid (98%)

0.1 mg/l Surfine WNT-A

Discovered that the addition of certain compounds can adjust the speed of the reaction and actually inhibit the formation of muddy sediment or sludge monovalent copper in the combined solution during the deposition process of copper according to the present invention, resulting in increased efficiency of the coating. These modifiers do not have the ability to control the reaction in the ammonia system disproportionation of the prior art. Suitable modifiers we use the Gent, wetting agent and dispersing agent, which is a free acid form of ethoxylated carboxylate fatty alcohol (a condensate of ethylene oxide) obtained from Finetex, Inc. of Elmwood Park, N. J.; Rochelle salt (mixed salt of potassium-sodium tartaric acid; glycine; Triethylenetetramine and Flocon 100, the means preventing the formation of scale, obtained from Pfizer Inc. Other modifiers include the following surfactants:

Modifier - Provider

P. E. Soapbark FA - Meer Corporation, North Bergen, NJ

Typically Extract 2F - Meer Corporation, North Bergen, NJ

Alkanol WXN - E. I. du Pont de Nemours, Wilmington DE

Alkanol XC - E. I. du Pont de Nemours, Wilmington DE

Triton X-155 - Rohm & Haas, Philadelphia, PA

Decersol OT 75 - American Cyanamid, Wayne, NJ.

Rexowet RW - Emkay Chemical Company, Elizabeth, NJ

Acrilev AM - Finetex, Inc., Spencer, NC

Eccosol P - Tex All Products, Pointe Claire Dorval, Quebec

Witconate SCS - Witco Chemical Corp., New York, NY

Witconol PS - Witco Chemical Corp., New York, NY

Antarox RC520 - GAF Corporation, New York, NY

These modifiers speed and inhibitors of the formation of deposits can be included in the above-described fourth component with a concentration of from about 0.1 to 10 g/l and the concentrations indicated in the examples of this patent. Also discovered that it is possible to obtain other advantages in the efficiency of the coating and/or the deposition is hydroxyethylenediaminetriacetate acid in an amount of about 50 g/l, boric acid in an amount of about 10 g/l, and surface-active agent, such as Atcowet C (company Bostik South, Inc. of Greenville, S. C.) in an amount of from about 0.1 to 1.0 g/L. All of the above supplements are best suited for the solution of the activator CU-300.

To implement the method of the present invention to obtain a metal layer of copper is prepared suitable substrate. In the example for the manufacture of mirrors, the glass surface sensibiliser or using salt tin (Sn2+and washing in 1% solution of palladium chloride or silver nitrate (when required copper mirror on glass), or covered with a layer of silver according to the patent '188 (Bahls) (when required silver mirror glass with copper base). Component CU-100 containing ions of bivalent copper, a reducing agent is a compound of nitrogen and antiaglomerate agent is mixed with the component CU-200, containing a solution of hydroxide of alkali or alkaline earth metal without ammonia, for a quick recovery of ions of bivalent copper hydroxide to monovalent copper. When the components contain copper sulfate, hydroxylamine sulfate and sodium hydroxide, the reaction to obtain a complex of monovalent copper is as follows:

< / BR>
Obrazovaniye to provide the most uniform deposition of copper. Preferred antiaglomerate agent is a polyol makes possible the dispersion of a hydroxide of monovalent copper in the form of small particles, which allows you to implement or spraying the mixture as a clear solution. the pH of the hydroxide monovalent copper is estimated at 10 to 11, and more than 12 when using an excess of sodium hydroxide. According to the present invention the monovalent hydroxide of copper obtained by the reaction of CU-100 and CU-200, can be used immediately or stored for future use.

For the deposition of elemental metallic copper to the desired substrate hydroxide monovalent copper is then mixed with the component CU-300, containing the activator, or the activator-modifier. When the component CU - 300 contains an acid activator, or the activator-modifier, the amount of acid used is chosen so that responsive to the output stream had a final pH below 7, preferably 1 to 4, more preferably 1 to 2. Component CU-300 can be mixed with hydroxide monovalent copper from the reaction of CU-100 and CU-200, merging them together above the surface, which is applied to the copper, or splashing them over the surface. Disproportionation monovalent ions of copper leads to the restoration and precipitated the train as oxidation remaining in the outgoing flow of the reaction solution of monovalent ions of copper to the divalent state.

The reaction temperature can be varied in the range of about 10 - 50oC, for optimum results, i.e., higher efficiency and minimum time sediment (slag), preferably in the range of about 15 - 30oC. higher temperatures tend to cause a decrease in the effectiveness of the coating, forming particles of metallic copper (muddy sediment or sludge), and no coating on the surface. Not counting education muddy sediment copper, the reaction efficiency also decreases with deposition due to the reaction of salts of monovalent copper with oxygen of the atmosphere. If necessary to increase the reaction efficiency this problem can be overcome by covering the reaction surface layer of gaseous nitrogen, carbon dioxide or other inert gas or virtually eliminating the oxygen in another way.

For the deposition of copper on they are vacuum surface on the inner side of the standard 250 ml laboratory glass beaker, with preferred concentrations of the components CU-100, CU-200 CU-300, listed above, apply the following procedure: take 37.5 ml CU-100 and add 9 ml of CU-200. Dilute with deionized water to 110 ml and well and has an extremely small particle size, the presence of polyol prevents their agglomeration. Then take 34 ml CU-300 and in a separate container diluted with deionized water to 100 ml.

Take 1 ml of the diluted solution CU-100 (to which was added a solution of CU-200), which can be called a solution, and 1 ml of the diluted solution CU-300, which can be called solution B, and simultaneously pour them into the silvered glass. The solutions carefully stir in for 10 s and left on the table at 50 C. On a layer of silver is deposited homogeneous film of copper. Then the solution is rinsed from the glass and drain excess water.

To calculate the efficiency of the reaction film of copper is then removed with a silver film by reaction with ammonium hydroxide solution in the presence of air until, until you dissolve the precipitate of copper, and the solution is titrated with 0.1 M solution of ethylenediaminetetraacetate, using as indicator end point titration Murexide. Then spent a solution of copper is saturated with ammonia and individually titrated on the copper content. After that, you can calculate the efficiency of the coating by the equation [T1/(T1+ T2)] 100%, where T1is the number of ml of the titrated solution used to determine besieged nom solution.

For the previously described preferred compositions of precipitated copper is homogeneous and mostly without streaks or spots. Found that the reaction efficiency is a value from 12 to 18% at normal atmospheric (aerobic) conditions or even higher under anaerobic conditions, well above the 11% achieved previously when using ammonium solution in the method of patent '842 (Sivertz and others).

The following illustrative examples are given to more in detail to illustrate the specific details of the practical application of the present invention. Specialists in this area will meet the equivalent procedures and quantity, therefore, the following examples are not intended to define the boundaries of the present invention, it defines the attached claims. All references to percentages in the examples throughout the description of the mean weight percent, unless otherwise indicated.

Example 1. Apply the method described above for deposition of copper on the glass, but the surface of the glass is not activated by the sensitizer of divalent tin, or not processed ions of palladium or silver to activate the surface. 3 ml and 3 ml solution In (sentence the Xia reddish metal sludge but education covering almost never happens. The measured pH of the reaction is equal to 1.7. Metal muddy sediment (sludge) is filtered off and determine the amount of the formed metallic copper, then calculate the efficiency of the process. Repeated several times, the tests give the average efficiency of formation of metal 32%. theoretical maximum for the disproportionation is 50%. This demonstrates the capabilities of the method, when the reaction is carried out on a catalytically activated surface or other on the conductive metal material such as a silver metal surface or other surfaces, which, as we all know are susceptible to coating non-electric (chemical) method.

Example 2. Repeat the procedure described in example 1, but now in the glass, sensitized and coated with metallic silver. CU-300 only contains sulfuric acid and citric acid (less than additive Surfine). After the mixture of solution a and solution To turning movement of a hand in the glass within 60 s, it was poured in the second raw glass. Now, the first glass contains a brilliant copper metallic coating over the silver. Determine the copper is non-electric (chemical), and the efficiency of the reaction makes the process possible.

Example 3. In order to show that the method is really non-electric, repeat the procedure described in example 1 in a glass, which is sensitized and then treated with dilute solution of palladium chloride or silver nitrate. Such glasses are experts in the field of coating by a chemical process called catalytically activated or supersensitivity. The glass actually looks transparent except for light gray hue, indicating that the surface superinsulation. When the mixture of solutions A and B added to the beaker and the solution rotate in a glass of motion within 60 s, the glass appears shiny coating of metallic copper, turning transparent glass copper glass mirror. This shows that the method is not described in the literature as galvanic displacement or application when submerged, which is usually demonstrated by placing an iron nail in acid copper sulfate solution to be applied on the nail copper coating.

Example 4. In order to show that the hydroxycarboxylic acid can be used as a salt, preferably sodium or ka is di (similarly, as in the previous examples), using CU-1C to obtain CU-100, followed by reaction of CU-100 and CU-200, as described above. In this case, the sediment monovalent copper has a yellow-orange color, this suggests that some ions to monovalent copper can be in the form of citrate monovalent copper, but chemical analysis shows that sediment monovalent copper is mainly a monovalent hydroxide copper. After that a solution of A monovalent copper reacts in the treated silver beaker with solution B obtained from a solution of CU-300, containing only 100 ml inorganic acids, namely, sulfuric acid, which is diluted with 3.3. When 1 ml of solution A and 1 ml of the solution To react for 1 min, get bright copper coating, the effectiveness of the coating is 5.9%, and the final pH of about 1.3. This shows that the usual reaction get when hydroxycarboxylic acid or its salt is or CU-275, or CU-100, provided that in CU-100 include some additional amount of inorganic acid to compensate for the alkalinity provided by sodium ions from salts of hydroxycarboxylic acids.

Example 5. The test is carried out in order to show retrieves whether additional advantages is available in the air. The copper deposition is carried out in a silvered glasses, as described previously. In one case, the reagent solutions A and B added to the glass in the presence of air. Get the efficiency of the coating 11%. In another case, the glass is continuously washed by nitrogen from a cylinder of compressed nitrogen. Reagents added to the beaker for 1 min in a continuous stream of nitrogen. In the second case, the reaction efficiency of the coating is 23%, showing that atmospheric oxygen is one of the reasons for the loss of efficiency of the coating, together with other reasons for the formation of metal sludge. This example shows that it is advisable to discuss the use of an inert gas to isolate the reaction surface (anaerobic conditions).

Example 6. A diluted solution prepared from A CU-100 and CU-200, except that the normal sodium hydroxide is substituted for sodium carbonate, mol for mol. In this case, the reaction of CU-100 and CU-200 takes approximately 30 minutes compared to the usual 1 - 2 min, when using sodium hydroxide. Then 1 ml of A solution reacts with 1 ml of the diluted solution B, as in the previous examples. Solution B is obtained from a sufficient number of CU-300 so that the pH of the reaction in the silvered glass SOS is Sardinia is allocated a certain amount of gaseous carbon dioxide, but not in sufficient quantity to act as a protective layer of inert gas. The release of gaseous carbon dioxide helps more uniformly dispersing the precipitate monovalent copper on the substrate. This suggests that other non-ammonia, alkaline compounds can be used as a third component, receiving additional benefits.

Example 7. The test is carried out to demonstrate whether you can use other hydroxycarboxylic acid instead of citric acid. Carry out the method of the previous examples, using CU-100 and CU-200 to obtain a dilute solution A. Various diluted solution B is obtained from various compositions of CU-300, all of which contain 80 ml/l of sulfuric acid, and each contains one of citric, tartaric or malic acid in the amount of 65 g/l, the reaction Time is 60 seconds, and the final pH value of about 1.1 to 1.2. The corresponding efficiency of the coating were 6.3, 9.1 and 18.2 percent for compositions containing, respectively, citric, tartaric and malic acid. This shows that the coating process of the present invention is not limited to only one hydroxycarboxylic acid, and variations in the choice of the acid depends on the experience of the ri efficiency in the same range, but dicarboxylic hydroxy acid (malic, citric, tartaric) tend to give a more smooth (smooth) film of copper.

Example 8. As the amount of citric acid used in the concentrated solution of SI-300 is a high-cost process, the amount of citric acid range, while maintaining such a quantity of sulphuric acid, which is enough to stay in the pH range from 1 to 3 and get a shiny copper coating. When use the technology of deposition of copper, as described in the previous examples, and vary the amount of citric acid from 40 to 120 g/l, the highest efficiency of the coating get from 50 to 70 g/l (the amount of sulfuric acid is fixed to 80 ml/l). For example, at 55 g/l of citric acid efficiency is 13%, with 40 g/l to 9%, and at 120 g/l - 8%. While the use of extremely low and extremely high amounts of citric acid may be less desirable in terms of efficiency, still produces bright copper coating. Similar tests with tartaric and malic acids give similar results. Therefore, the method of the present invention is not dependent on the concentration of hydroxy carboxylic acid. However, should the erated within the desired range, usually from 1 to 3.

Example 9. It is desirable to prepare a diluted solution And hydroxide monovalent copper with the least amount of agglomerates. Found that the preferred technology is the deposition rate of the hydroxide monovalent copper under the influence of gravity in a stationary vertical glass cylinder. A solution of A hydroxide of monovalent copper with minimal or very slow deposition rate also gives the most uniform deposition of copper, when thin layers of copper are examined under transmitted light from the lamp high power. Although the use antiglomerular agent is not required to obtain a copper coating, they are highly desirable to obtain a uniform layer when the process is used for the manufacture of copper mirrors or copper plating of the reverse side of the silver mirrors. Antiglomerular substances must be contained in one concentrated solutions of CU-275, CU-1C or CU-200 before they will be diluted and will respond, giving a solution of A monovalent copper. In this way, it is desirable to add to the reaction of a substance that allows the molecules of hydroxide monovalent copper is preferable to form hydrogen bonds with those who conducted the monitoring of the deposition rate after 15 minutes. In this case, CU-275 were made additives to obtain solution A. the following results are Obtained where the percentage deposition refers to the height of the column of pure solution relative to the total height of the liquid column, and a lower percentage indicates better dispersion and less allamaraju (see table).

Additional studies show that the preferred range of the content of these polyols is from about 10 to 100 g/l in solution CU-275, and investigated the range of from about 1 to 200 g/l shows that it is preferable for the content of the polyol from 65 to 75 g/L. In all cases, the use of polyols results in a more uniform deposition of metallic copper.

Example 10. The study of the way the disproportionation of copper in the absence of ammonia present invention on a horizontal, continuously moving mirror that represents the pipeline, which typically uses ammonia method described in patent '842 (Sivertz and others). Sheets of soda-lime float glass is placed on the loading end of the conveyor with the atmospheric side facing up. All procedures for the manufacture of mirrors spend on this upper side, the procedure involves first cleaning sensibility square foot (807 mg/m2), this value is inside a typical modern silver glass mirrors range 70 - 90 mg square foot (750 - 970 mg/m2). After water by-products of the process of silvering blow out the glass and then washed with deionized water, glass, plated with silver, put a layer of copper, which moves along a mirror, forming a pipeline.

In this test, the present invention previously described reagents for the deposition process of copper: CU-100, CU-200 CU-300 (using citric acid) is continuously diluted with water, applying a well-known device that measures the download speed of the reactants and the rate of flow of water to dilute before applying the reagents they are vacuum on the surface. In this particular case, silvered glass passes under the conveyor section for applying copper to a speed of 62 sq. ft/min (5.8 m2/min). CU-100 and CU-200 finish with the speed of 305 and 73 ml / min, respectively, in the same water flow 945 ml / min and allowed to react for about 3 min when passing through a small reaction chamber for formation of a dilute solution A. CU-300 finish with the speed of 305 ml/min water flow 1130 ml/min for the formation of Rabba is only when they are vacuum applied to the glass surface, when it passes under the spray. The spray nozzle is moved back and forth by means of the transporting device to obtain uniform distribution of the mixed solutions A and B on the silvered glass. The initial color of the reagents on the silver surface is dull orange, begins immediately after the deposition of metallic copper on silver, transforming the appearance of silver-plated surface to surface with copper coating. The measured pH of the reaction is 1.5. After 1 min of reaction reagents washed with deionized water and dried mirror, direct the jet of clean air. Get bright copper coating, continuous, without visible defects. It is found that the weight of the deposited copper is 34 mg/sq ft (366 mg/m2). The calculated efficiency of deposition of copper for the reaction is about 13%. Dried and covered with silvered copper glass mirror continues to move down the conveyor section for applying a protective layer of paint and then in a drying oven to obtain a final silver glass mirror. When checking for 300 h in the standard test (known in the manufacture of mirrors) with a sprinkling of 20% salt is found that the samples of mirrors resistant to corrosion at least in the RV). Coming from the process of applying copper stream passes through the ion exchange column for the regeneration of copper ions, and ammonia output stream after pH adjustment discharged into the sewer system, thus avoiding the costly removal of ammonia or procedure of decomposition.

The present invention provides a highly stable complex hydroxide of a monovalent copper which does not affect the quality ageing in the atmosphere. As a result, this process can be used without using complex equipment used in the prior art, which keeps the solution in an atmosphere containing no oxygen. Hydroxide monovalent copper can be obtained directly before use and store in an open container without the need to exclude oxygen. When copper is applied on the desired activated substrate, a hydroxide solution of monovalent copper can be added to the tank, open to the air, dispersing mixer and then pumped into the spray distribution on the substrate. Similarly, the solution of the activator can be added to the outdoor air tank for simultaneous sputtering on the substrate with a solution hydroxide together right in front of the spray and spray from one nozzle or orifice. The reaction rate can be adjusted and improve overall efficiency. The film deposited metallic copper is more resistant to corrosion and not soon dims under the action of water vapor. Ultimately, the ammonia was removed from the process and the amount of activator is an organic acid significantly reduced, thus providing significant advantages in terms of environmental protection and cost.

Thus, it should be clear that the above objectives, among those apparent from the preceding description, are efficiently attained and the above construction can make some changes without departing from the spirit and scope of the present invention, we mean that all the materials contained in the above description shall be interpreted as illustrative and not restrictive examples.

While the invention is illustrated and described in what is considered the most practically important and preferred options, recognize that many possible variations that meets the spirit and scope of the invention, therefore, the appended claims corresponds to a range of equivalents.

1. The method of deposition of metallic copper on the catalytically AC ions of bivalent copper reducing agent, does not contain ammonia and containing the hydroxylamine or its salt, and subsequent disproportionation compounds obtained with the use of the activator, characterized in that the recovery is carried out in the presence of water-soluble alkaline hydroxide or alkaline earth metal with getting hydroxide monovalent copper subjected to disproportionation.

2. The method according to p. 1, characterized in that the recovery of ions of bivalent copper exercise adding to aqueous solution antiglomerular agent to control the dispersion of a hydroxide of monovalent copper.

3. The method according to p. 2, characterized in that as antiglomerular agent used polyol.

4. The method according to p. 2, characterized in that antiaglomerate agent selected from the group consisting of dextrose, fructose, glucono-Delta-lactone, glucoheptonate sodium, L-sorbose, invert sugar, sucrose, D-galactono-gamma-lactone, 2-keto-D-gluconic acid, glycine, D-mannose and D-galactose.

5. The method according to p. 1, characterized in that the activator is used hydroxycarboxylic acid or its salt in an amount of less than about 1 mol per 1 mol of hydroxide monovalent copper.

7. The method according to p. 2, characterized in that as antiglomerular agent used to sorbose.

8. The method according to p. 1, characterized in that as antiglomerular agent used invert sugar.

9. The method of deposition of metallic copper on a catalytically activated surface, including the provision of ions of bivalent copper in aqueous solution, the recovery of ions of bivalent copper reducing agent ammonia, and subsequent disproportionation compounds obtained with the use of the activator comprising hydroxycarboxylic acid or its salt, wherein the restoring is performed in the presence of hydroxide of alkali or alkaline earth metal with getting hydroxide monovalent copper subjected to disproportionation, and disproportionately carried out at a flow rate hydroxycarboxylic acid or its salt in an amount of not more than about 1 mol to 1 mol g containing ammonia, apply the hydroxylamine or its salt.

11. The method according to p. 9, characterized in that as an activator comprising hydroxycarboxylic acid or its salt, is used as an activator, optionally containing inorganic acid.

12. The method according to p. 11, characterized in that as a hydroxycarboxylic acid is used citric acid.

13. The method according to p. 11, characterized in that as a hydroxycarboxylic acid is used malic acid.

14. The method according to p. 11, characterized in that as a hydroxycarboxylic acid is used tartaric acid.

15. The method according to p. 9, characterized in that the recovery of ions of bivalent copper exercise adding to aqueous solution antiglomerular agent to control the dispersion of a hydroxide of monovalent copper.

16. The method according to p. 15, characterized in that as antiglomerular agent used polyol.

17. The method according to p. 15, characterized in that antiaglomerate agent selected from dextrose, fructose, glucono-Delta-lactone, glucoheptonate sodium, L-sorbose, invert sugar, sucrose, D-galactono-gamma-lactone, 2-keto-D-gluconic acid, glycine, D-mannose and D-galactose.

18. With the emnd salt of copper.

19. The method according to p. 9, wherein the hydroxycarboxylic acid or its salt add the speed modifier selected from the group consisting of Surfine, representing the free acid form of ethoxylated carboxylate of a fatty alcohol, potassium tartrate sodium, glycine, Triethylenetetramine and Flocon 100, which surface-active anionic polyacrylate.

20. Composition for the deposition of copper on a substrate containing an aqueous solution containing ions of bivalent copper, an aqueous solution of reducing agent ions of bivalent copper, ammonia-containing hydroxylamine or its salt at a minimum concentration of about 25 g/l to restore ions of divalent copper ions to monovalent copper, an aqueous activator solution containing hydroxycarboxylic acid or its salt, amine or inorganic acid in combination with a hydroxycarboxylic acid or its salt, or an amine for the disproportionation of sediment monovalent copper and deposition of copper on a substrate, characterized in that that it further comprises an aqueous solution of hydroxide of alkali or alkaline earth metal, and components necessary to restore the divalent ions of copper, it contains in molar is trichomania fact, that it further comprises antiaglomerate agent to control the dispersion of a hydroxide of monovalent copper.

22. The composition according to p. 21, characterized in that as antiglomerular agent it contains a polyol.

23. The composition according to p. 21, characterized in that as antiglomerular agent it contains an agent selected from the group consisting of dextrose, fructose, glucono-Delta-lactone, glucoheptonate sodium, L-sorbose, invert sugar, sucrose, D-galactono-gamma-lactone, 2-keto-D-gluconic acid, glycine, D-mannose and D-galactose.

24. The composition according to p. 21, characterized in that it contains antiaglomerate agent in the amount of 1 to 200 g/l to 1 mol used salts of copper.

25. The composition according to p. 20, characterized in that the aqueous solution of the activator contains a hydroxycarboxylic acid or its salt in an amount of not more than about 1 mol per 1 mol of hydroxide monovalent copper.

26. The composition according to p. 20, characterized in that the aqueous solution of the activator contains a speed modifier selected from the group consisting of Surfine, representing the free acid form of ethoxylated carboxylate of a fatty alcohol, potassium tartrate-three-is>27. The composition according to p. 21, characterized in that as antiglomerular agent it contains sorbose.

28. Composition for the deposition of copper on a substrate containing an aqueous solution containing ions of bivalent copper, an aqueous solution of reducing agent ions of bivalent copper, ammonia-containing nitrogen compounds with a minimum concentration of about 25 g/l to restore ions of divalent copper ions to monovalent copper, an aqueous activator solution containing hydroxycarboxylic acid or its salt, characterized in that it further comprises an aqueous solution of hydroxide of alkali or alkaline earth metal hydroxycarboxylic acid or its salt it contains in an amount of not more than about 1 mol per 1 mol of hydroxide monovalent copper, and the components necessary for the recovery of ions of bivalent copper, it contains in molar quantities sufficient to recover essentially all of the copper ions.

29. The composition according to p. 28, characterized in that as a hydroxide of an alkali metal it contains sodium hydroxide.

30. The composition according to p. 28, wherein the activator further comprises an inorganic acid.

31. Com is the position of p. 28, characterized in that the activator it contains malic acid.

33. The composition according to p. 28, characterized in that the activator it contains tartaric acid.

34. The composition according to p. 28, characterized in that the solution of reducing agent ions of bivalent copper further comprises antiaglomerate agent to control the dispersion of a hydroxide of monovalent copper.

35. The composition according to p. 34, characterized in that as antiglomerular agent it contains a polyol.

36. The composition according to p. 34, characterized in that as antiglomerular agent it contains an agent selected from the group consisting of dextrose, fructose, glucono-Delta-lactone, glucoheptonate sodium, L-sorbose, invert sugar, sucrose, D-galactono-gamma-lactone, 2-keto-D-gluconic acid, glycine, D-mannose and D-galactose.

37. The composition according to p. 34, characterized in that it contains antiaglomerate agent in the amount of 1 to 200 g/l to 1 mol used salts of copper.

38. The composition according to p. 28, characterized in that the aqueous solution of the activator further comprises a speed modifier selected from the group consisting of Surfine representing free sour the amine and Flocon 100, which surface-active anionic polyacrylate.

39. The composition according to p. 28, characterized in that the aqueous solution of the activator further comprises an additive selected from the group consisting of antioxidants, acid complexing agents, boric acid and surface active agents.

 

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FIELD: electrolytic bath for electrolysis aluminum production, in particular cathode, casing of sidewalls.

SUBSTANCE: claimed material contains open-porous or gauze ceramic structure, wherein surface of said structure under using is exposed by melted aluminum and wetted therewith. Structure is made of ceramic material which is inert and resistant to melted aluminum such as alumina, and aluminum-wetted material including metal oxide and/or partially oxidized metal such as manganese, cobalt, nickel, copper or zinc, which is capable to interact with melted aluminum to produce surface layer, containing alumina, aluminum and metal, obtained from metal oxide and/or partially oxidized metal. Ceramic structure includes coating from aluminum-wetted material carried on inert and resistant material or comprises mixture of inert and resistant material and aluminum-wetted ceramic material.

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34 ex, 3 dwg, 4 ex

FIELD: chemical industry; other industries; methods and the devices used for treatment of the containers coating.

SUBSTANCE: invention is pertaining to method and the device used for treatment of the containers coating, in particular, to the method and conforming device used for drying of the protecting coatings on the containers. The method and the device are intended for drying of the coatings of the containers manufactured out of the thermoplastic material. The method includes feeding of the indicated containers through the furnace divided into two sections: in the first section the bulk of the dissolvent of the coating is removed by means of heating up of the paint by the lamp of the W radiance in the infrared radiation, while the containers temperature is controlled by means of the air flow; on the second section the remained dissolvent is removed by means of usage of the indicated air flow coming from the first section of the furnace. The technical result of the invention consists in improvement of the known methods and devices used for drying of the deposited on the containers protective coatings manufactured out of the thermoplastic material, excluding their overheating.

EFFECT: invention ensures improvement of the known methods and devices used for drying of the deposited on the containers protective coatings manufactured out of the thermoplastic material at exclusion of their overheating.

14 cl, 2 dwg

FIELD: production methods.

SUBSTANCE: method of application of one or more layers of protection gum to the container side surface, in particularity bottles, consists in containers directing to the device of layer application, conveying transporting of bottles through the area of layer application, where containers are flooded in the mixture of for layer application, removing of the bottles from the mixture, the removing of the odd of mixture from the surfaces of the bottles, then removing of the mixture resolvent, the process of hardiness and the drying of the layer gum. The device for the layer application is the one device for the conveying transporting of bottles or containers through the device, the device for the layer application situated after the area of clipping the bottles, the device for rotating of clipping devices, the device for gum drying contained in the colors.

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20 cl, 6 dwg

FIELD: process.

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2 cl, 5 dwg, 1 tbl, 2 ex

FIELD: technological processes.

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2 cl, 3 dwg

FIELD: process engineering.

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8 cl, 8 dwg

FIELD: process engineering.

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34 cl, 2 ex, 4 dwg

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FIELD: metallurgy.

SUBSTANCE: invention relates to powder metallurgy, in particular to the methods of production of high porous cellular materials (HPCM) intended for use as filters, acoustic absorbers, catalyst carriers, heat exchange systems, structural materials working under high temperatures, and can be used in power engineering, machine building, chemical and other industries. The method includes preparation of suspension of the mixture of powders based on chromal, the suspension application to the porous polymer material, the organic substances removal by heating with production of the blank, the blank sintering, at that on the blank after its sintering the chrome oxide Cr2O3 is applied, and secured in volume and on surface of the blank cell by sintering.

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4 cl, 1 ex

FIELD: chemistry.

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9 cl, 4 dwg

FIELD: application of metallic; chemical copper plating of metal and dielectric parts, mechanical rubber goods in particular.

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EFFECT: enhanced elasticity of copper coat; enhanced adhesion with surface to be coated; increased rate of reaction.

2 tbl, 1 ex

FIELD: application of metallic coatings, possibly chemical deposition of composition type copper coatings onto steel parts that may be used in electric, chemical industry branches, in machine engineering.

SUBSTANCE: solution contains copper sulfate, sodium potassium tartrate, sodium sulfate, sodium hydroxide, Formalin, Aerosil and 20% aqueous solution of polyacrylamide at next relation of ingredients (g/l): copper sulfate, 4 - 5; sodium potassium tartrate, 20 - 22; sodium sulfate, 15 - 16; sodium hydroxide, 10 - 12; Formalin, 20 -24; Aerosil, 0.2 - 0.3; 20% aqueous solution of polyacrylamide, 0.5 - 3.

EFFECT: improved wear resistance, corrosion resistance in sea atmosphere due to increased thickness of coating, lowered friction factor.

1 ex, 2 tbl

FIELD: technological process.

SUBSTANCE: invention is related to methods of copper coating of plastics, in particular, polymer composition materials on the basis of carbon fibers and may be used in manufacture of furniture fittings, household appliances and utensils, in automobile and radio industries. Method includes preparation of polymer composition material surface - cleaning, degreasing, immersion and soaking of polymer composition material for 40 - 60 minutes in acid solution of electrolyte with the following composition, g/l: copper sulfate 195 - 235, concentrated sulfuric acid 50 - 60, sodium chloride 0.07 - 0.15 and electrochemical depositing of copper in the same electrolyte at temperature of 20 - 24°C, current density of 5.0 - 6.0 A/dm2 for 5-10 minutes, pH of electrolyte - 1.

EFFECT: allows to increase purity of productivity, to simplify copper coating process, to increase environmental safety and economic efficiency of production.

2 dwg, 2 tbl, 13 ex

FIELD: technological processes.

SUBSTANCE: invention is related to technology for production of metalised woven and nonwoven materials, and may be used for production of catalysts, and also for production of decorative and finishing materials. Method includes previous chemical activation of coated material surface, using as activator glyoxal acid and/or oxalic acid. Then chemical metallisation is carried out, which is realised from solution containing bluestone. Stabiliser used is tetraethylene glycol, and reducer - glyoxal. Sodium hydroxide is used in solution to maintain required acidity.

EFFECT: invention provides for production of metalised dispersed woven and nonwoven materials using simplified technology, with simultaneous cheapening and provision of production safety due to use of proposed ingredients and their certain ratio.

2 ex

FIELD: process engineering.

SUBSTANCE: invention relates to metal-working and can be used in metallurgy, machine building and other industrial branches for processing wire, strips, tubes and other various-section products. Proposed method comprises, prior to applying copper from copper-containing solutions, coppering and processing products after coppering. Note here that at least a part of product processing process, prior to coppering, is performed by at least single vacuum-arc processing of a product-cathode, and at least with the help of electrode-anode. Note here that said vacuum-arc processing is performed in conditions of product cleaning without oxidising its surface in conditions of cleaning with oxidising at least a part of product surface, while blue copperas solution represents copper-containing solution.

EFFECT: perfected production of coppered metal, higher efficiency and coppered products transfer rate, higher quality of cleaning.

5 cl, 4 dwg

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