The method of chemical deposition of tin coatings on parts of copper or its alloys (options)

 

(57) Abstract:

The invention relates to applied chemistry, in particular to the chemical treatment of metallic material by surface interaction with the reaction liquid, and can be used in the plating of copper products and its alloys to protect them from harsh environments. In the first embodiment of the invention the method includes processing the parts in an aqueous solution containing sulfuric acid, thiourea, tin douglaston two-water, while the working solution pre-incubated at a temperature of 17-30C within 1-30 days, and before processing in the working solution produce etching parts in 18-25% solution of sulfuric or hydrochloric acid for 20-35 seconds subsequent processing in the working solution is performed without prior washing of parts; in the second variant of the invention the method includes processing the parts in a working aqueous solution containing hydrochloric acid, sodium chloride, thiourea, tin douglaston two-water, while working solution pre-incubated at a temperature of 17-30C within 1-30 days, and before processing in the working solution produce etching parts in 18-25% hydrochloric acid solution for a result of the implementation of both variants of the invention increase the density and uniformity of the coating and thereby increases its resistance to aggressive environment. 2 S. and 6 C.p. f-crystals.

The invention relates to applied chemistry, in particular to the chemical treatment of metallic material by surface interaction with the reaction liquid, and can be used in the plating of copper products and its alloys to protect them from harsh environments.

Known method of applying a tin coating on articles of copper or copper alloys by the interaction of these products with an aqueous solution containing soluble salts of tin, under pressure by means of compressed gas, in particular hydrogen, US 3072499.

The disadvantage of this method is the high energy intensity of the process, due to the need of the use of gas under pressure; the use of hydrogen leads to a high risk method.

Known method of applying a tin coating on the surface of copper or copper alloys by immersing these products in an alkaline aqueous solution containing a salt of divalent tin and cyanide, US 2159510.

A fundamental and very serious disadvantage of this method is the use of such highly toxic substances like cyanide. Working with these substances require is ologie.

There is also known a method of chemical deposition of tin coatings on parts of copper and its alloys by keeping these details in a working solution containing tin douglaston two-water, thiourea, sulfuric acid and Volgoneft; for solution use cold drinking water. The working solution is proposed to use immediately after preparation”. Processing of workpieces in the working solution is performed without prior etching them in a solution of sulfuric acid, RU 2121013.

This method is adopted for the prototype of the first variant of the present invention.

The disadvantages of the method described in the text of the description of this patent, are the following factors.

Since, as indicated at S. 3 of the description, the working solution is used immediately after its preparation, it has not achieved the required gradient of bulk density, because the diffusion rate of dissolved in the working solution of substances not quickly provide them with a uniform volumetric concentration in solution.

This leads to the unsatisfactory quality of the coating due to its irregularity.

In addition, on the surfaces of the workpiece inevitably have okii water, containing impurities. In the method prototype cleaning etching is missing, although, of course, known from other sources; however, all known to the applicant how after etching parts necessarily washed, which inevitably leads to the formation of thin oxide films.

For the prototype of the second variant of the present invention adopted the method of chemical deposition of tin coatings on parts of copper and its alloys by keeping these details in a working solution containing tin douglaston two-water, thiourea, hydrochloric acid and sodium chloride, see GOST 9.305-84; the mortar in cold drinking water and used immediately after preparation; the preliminary etching of the parts in a solution of hydrochloric acid is not provided.

The disadvantage of this technical solution is the same as that of the prototype method of the first variant of the invention: in the working solution is not achieved by the time of its use of the required gradient of bulk density, resulting in uneven coating, the coating has a high porosity due to the formation of oxide films.

The task of both variants of the present invention is to increase the density and According to the invention this task in the first case solved by in the method of chemical deposition of tin coatings on parts of copper or its alloys by processing them in an aqueous solution containing sulfuric acid, thiourea, tin douglaston two-water, working solution pre-incubated at a temperature of 17-30C within 1-30 days, and before processing in the working solution produce etching parts in 18-25% solution of sulfuric or hydrochloric acid for 20-35 seconds, and the subsequent processing in the working solution is performed without prior washing of parts; it is preferable to use distilled water; the processing of workpieces in the working solution can be implemented within 50-130 min, the temperature of the working solution is maintained in the range from 20 to 35C.

In the second variant of the invention the problem is solved due to the fact that in the method of chemical deposition of tin coatings on parts of copper or its alloys by processing them in a working aqueous solution containing hydrochloric acid, sodium chloride, thiourea, tin douglaston two-water, working solution pre-incubated at a temperature of 17-30C within 1-30 days, and before processing in the working solution produce etching parts in 18-25% ratspredlozhenij wash parts; it is preferable to use distilled water; the processing of workpieces in the working solution can be implemented within 50-130 min, the temperature of the working solution is maintained in the range from 65 to 75S.

The applicant has not identified the sources containing information about technical solutions, identical to the present invention, which allows to make a conclusion about its compliance with the criterion of "novelty".

Implementation characteristics of the invention, in particular the preliminary curing solution at certain temperatures, allows to provide the same volumetric concentration throughout the mass of the solution. The specified temperature range, and the exposure time are essential. When the temperature of the solution is less 17C process of dissolution and diffusion components practically stops; at temperatures above 30C dramatically increases the speed of the interaction of sulfuric or hydrochloric acid with thiourea and salts of tin, which leads to the so-called “aging solution and, as a consequence, a significant increase in porosity and uneven coverage.

When the exposure of the working solution of any size less than 1 day, the goal of exposure is not achieved, and if the shutter speed is more than 30 the volume of the working solution. In particular, the solution volume 1-5 DM3enough to withstand 1 day, and when the amount of 100 DM3the exposure time increases to 2-5 days.

In the first variant of the method using a solution containing the following components, wt%:

H2SO43,0-4,0

Thiourea 3,5-4,5

SnCl2·2H2O l 0-l,5

Distilled water the Rest

in the second embodiment, the working solution has the following composition, wt.%:

HCl 1,5-2,2

NaCl 6,5-8,5

Thiourea 8-10

SnCl2·2H2O l,3-2,3

Distilled water the Rest

Immersion of the parts in the working solution after etching without pre-washing prevents the formation of oxides and remains active surface.

Use for a method of distilled water eliminates the influence of impurities, particularly iron ions, magnesium, calcium.

The applicant has not identified any sources of information containing data about the impact of an alleged distinguishing signs on achieved as a result of their implementation of the technical result. This, according to the applicant demonstrates compliance with this technical solution criteria is lustered examples 1 and 2, and implementation of the second option (PP 5-8) - examples 3 and 4.

Example 1.

Pre-polished copper plate 75303 mm was treated in a 1 DM3an aqueous solution containing, wt.%:

H2SO43,0

Thiourea 3,5

SnCl2·2H2O 1,0

Distilled water the Rest

The working solution was pre-seasoned at t=17C within 1 day. The copper plate before immersion in the solution was subjected to etching in an 18% solution of H2SO4within 20 s, the working solution was loaded without prior washing and was kept there for 50 minutes at t=20C. The stability of the formed coating in N2SO4with a density of 1.4 g/cm3at t=60C amounted to 36 hours.

Example 2.

Was carried out covering 5 brass plates with the same dimensions as in example 1.

The volume of working solution - 20 DM3composition, wt.%:

H2SO43,5

Thiourea 40

SnCl2·2H2O 1,5

Distilled water the Rest

Pre-exposure of working solution - 5 days at a temperature of - 25C.

Wafers were subjected to was prevarications it 100 minutes at to=35C.

The coating is resistant to H2SO4with a density of 1.4 g/cm3at t=60C for 48 hours.

Example 3.

Copper plates, 5 pieces, with dimensions 75303 mm were treated in 20 DM3an aqueous solution containing, wt.%:

Hydrochloric acid 2,0

Sodium chloride 7,0

Thiourea 9,0

SnCl2·2H2O 2,0

Distilled water the Rest

Pre-exposure of working solution to 10 days at t=20S. The preliminary etching in 30% Hcl for 25 sec.

In the working solution, the plate was immersed without washing and kept for 120 minutes at a temperature of 65 degree Celsius.

The coating is resistant to H2SO4with a density of 1.4 g/cm3at t=60 ° C for 34 hours.

Example 4.

20 plates of copper with dimensions 75303 mm were treated in 100 DM3an aqueous solution containing, wt.%:

HCl 1,7

NaCl 8,0

Thiourea 9,0

SnCl2·2H2O 2,0

Distilled water the Rest

Pre-exposure of the solution to 3 days, t=25S. Etching in 25% model HC1 produced within 35 C. the processing Time in the working solution of 120 minutes at t=75S.

In the work of the WG/cm3at t=60C for 48 hours.

1. The method of chemical deposition of tin coatings on parts of copper or its alloys by processing them in a working aqueous solution containing sulfuric acid, thiourea, tin douglaston two-water, characterized in that the working solution pre-incubated at a temperature of 17-30C within 1-30 days, and before processing in the working solution produce etching parts in 18-25% solution of sulfuric acid within 20-35 with subsequent processing in the working solution is performed without prior washing of parts.

2. The method according to p. 1, characterized in that use distilled water.

3. The method according to p. 1 or 2, characterized in that the processing of workpieces in the working solution is carried out for 50-130 minutes

4. The method according to p. 3, characterized in that the support temperature of the working solution in the range from 20 to 35C.

5. The method of chemical deposition of tin coatings on parts of copper or its alloys by processing them in a working aqueous solution containing hydrochloric acid, sodium chloride, thiourea, tin douglaston two-water, characterized in that the working solution is maintained at a pre-tempersture hydrochloric acid within 20-35, thus, the subsequent processing in the working solution is performed without prior washing of parts.

6. The method according to p. 5, characterized in that use distilled water.

7. The method according to p. 5 or 6, characterized in that the processing of workpieces in the working solution is carried out for 50-130 minutes

8. The method according to p. 7, characterized in that the support temperature of the working solution in the range from 65 to 75S.

 

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