CN110592626A - Cyanide-free electroplating brass liquid and use method thereof - Google Patents

Cyanide-free electroplating brass liquid and use method thereof Download PDF

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Publication number
CN110592626A
CN110592626A CN201911001769.4A CN201911001769A CN110592626A CN 110592626 A CN110592626 A CN 110592626A CN 201911001769 A CN201911001769 A CN 201911001769A CN 110592626 A CN110592626 A CN 110592626A
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China
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brass
electroplating
cyanide
solution
free
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CN201911001769.4A
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田志斌
詹益腾
邓正平
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Novel Material Science And Technology Co Ltd Is Inspired Confidence In Guangzhou Three
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Novel Material Science And Technology Co Ltd Is Inspired Confidence In Guangzhou Three
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Priority to CN201911001769.4A priority Critical patent/CN110592626A/en
Publication of CN110592626A publication Critical patent/CN110592626A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/58Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper

Abstract

The invention belongs to the technical field of electroplating, and particularly relates to a cyanide-free electroplating brass liquid and a using method thereof. The cyanide-free electroplating brass liquid takes deionized water as a solvent, and comprises the following components: 15-35 g/L copper sulfate, 8-20 g/L zinc sulfate, 120-200 g/L pyrophosphate, 1-3 g/L auxiliary complexing agent 10-20 g/L, pH regulator, 20-40 g/L conductive agent, 0.01-0.02 g/L main brightener, 0.001-0.1 g/L auxiliary brightener and 0.1-1 g/L methyl glucitol polyether. According to the invention, by adding the methyl glucitol polyether, the obtained brass plating layer is uniform in color and compact, the problems that the color and luster of the plating layer are difficult to control and the current density range is narrow when pyrophosphate is used as a cyanide-free electroplating solution complexing agent are solved, and the electroplating efficiency is improved. The brass electroplating solution is safe and environment-friendly, has good electroplating effect, and is favorable for popularization and utilization of brass electroplating.

Description

Cyanide-free electroplating brass liquid and use method thereof
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to a cyanide-free electroplating brass liquid and a using method thereof.
Background
The brass is an alloy consisting of copper and zinc, and the color of the brass is golden and exactly like gold, so that the cost of gold as decoration is reduced, and the brass is an ideal surface decoration material. The surface of an object is usually decorated by electroplating with a plating solution containing Cu-Zn alloy. In the brass electroplating process, the brass plating layer is divided into two categories of cyanogen-containing electroplating liquid and cyanogen-free electroplating liquid, the brass plating layer obtained by electroplating brass by using the cyanogen-containing electroplating liquid has good bonding force, fine crystallization and wide application, but the cyanogen-containing electroplating liquid is a highly toxic substance and is easy to decompose to generate hydrogen cyanide gas, once the cyanogen-containing electroplating liquid is absorbed by a human body, the cyanogen-containing electroplating liquid cannot be cured, the life of an operator is seriously threatened, and the emission of the cyanogen-containing electroplating waste liquid can cause pollution; cyanide-free electroplating solutions include pyrophosphate systems, HEDP systems, citrate systems, ethylenediamine systems, tartrate systems, oxalate systems, etc., but these cyanide-free electroplating systems have problems of narrow process parameter ranges, unstable coating colors, poor brightness, etc. The pyroglutate system in the cyanide-free electroplating solution has strong capability of complexing zinc and copper ions, the process is clean, and the required brass plating layer can be obtained by adding proper additives and auxiliary coordination agents, so that the brass electroplating solution is expected to be industrially applied. However, the strong deposition of pyrophosphate on copper leads to high requirement on current density range, copper is firstly precipitated at low current density, and the surface of the coating is rough and even scorched at slightly high current density, so that proper additives or auxiliary coordination agents are required to be added to inhibit the preferential precipitation of copper, and the brass alloy coating with wide current density range can be obtained.
The Chinese invention patent CN105463535A provides an electroplating method of cyanide-free copper-zinc electroplating solution containing ionic liquid, the electroplating solution comprises pyrophosphate, copper sulfate, zinc sulfate, glycerol, ionic liquid and the like, and the good ionic conductivity and thermal conductivity of the ionic liquid are utilized, so that the obtained brass plating layer has good bonding force with a substrate and uniform and bright color. However, most of the ionic liquids are very easy to absorb water, so strict water removal and oxygen removal treatment are required in the electrodeposition process, the cost for synthesizing the ionic liquid is high, and the application range is limited.
In order to solve the problems of unstable quality and narrow current density range of the electroplated brass in a pyrophosphate system, the electroplated brass liquid with economy, environmental protection and good electroplating effect and the use method thereof are provided.
Disclosure of Invention
The invention aims to provide cyanide-free electroplated brass liquid and a using method thereof, wherein a brass coating with uniform color can be obtained by adding an auxiliary brightener methyl glucitol polyether, and the problem of narrow range of the deposition current density of pyrophosphate cyanide-free electroplated brass can be solved.
The specific technical scheme for solving the technical problems is as follows:
the cyanide-free electroplating brass liquid is characterized in that deionized water is used as a solvent, and the cyanide-free electroplating brass liquid comprises the following components: 15-35 g/L copper sulfate, 8-20 g/L zinc sulfate, 120-200 g/L pyrophosphate, 1-3 g/L auxiliary complexing agent 10-20 g/L, pH regulator, 20-40 g/L conductive agent, 0.01-0.02 g/L main brightener, 0.001-0.1 g/L auxiliary brightener and 0.1-1 g/L methyl glucitol polyether.
Preferably, the cyanide-free electroplating brass liquid is characterized by taking deionized water as a solvent and comprising the following components: 20-25 g/L of copper sulfate, 12-15 g/L of zinc sulfate, 140-160 g/L of pyrophosphate, 15-20 g/L, pH g/L of auxiliary complexing agent regulator 1.8-2.2 g/L, 30-35 g/L of conductive agent, 0.05-0.01 g/L of main brightener, 0.005-0.1 g/L of auxiliary brightener and 0.3-0.5 g/L of methyl glucitol polyether.
Preferably, the cyanide-free electroplating brass liquid is characterized in that the auxiliary complexing agent is at least one of potassium citrate, sodium citrate, potassium oxalate and sodium oxalate.
Preferably, the cyanide-free electroplating brass liquid is characterized in that the pH regulator comprises at least one of sodium hydroxide and potassium hydroxide.
Preferably, the cyanide-free electroplating brass liquid is characterized in that the conductive agent comprises at least one of potassium chloride, sodium chloride, potassium carbonate, dipotassium hydrogen phosphate and potassium nitrate.
Preferably, the cyanide-free electroplated brass liquid is characterized in that the main brightener is at least one of sodium mercaptoimidazolepropanesulfonate, sodium 3- (benzothiazole-2-mercapto) propanesulfonate and sodium 2-mercapto-5-benzimidazolesulfonate.
The mercapto imidazole sodium propanesulfonate, the 3- (benzothiazole-2-mercapto) sodium propanesulfonate and the 2-mercapto-5-benzimidazole sodium sulfonate are all mercapto heterocyclic compounds which are favorable for forming crystal nuclei in the electroplating process, so that the crystal nuclei are distributed compactly, and smooth coatings with smooth surfaces are favorably obtained.
Preferably, the cyanide-free electroplating brass liquid is characterized in that the auxiliary brightening agent is 1-benzylpyridinium-3-carboxylate.
The auxiliary brightener 1-benzylpyridinium-3-carboxylate is a compound containing quaternary ammonium ions, and the compound containing the quaternary ammonium ions can effectively inhibit the discharge speed of zinc ions, particularly the discharge speed in a high current density area, so that the bright current density range can be expanded to a high current density area to obtain a very bright zinc coating, and the quaternary ammonium compound can also be used as a copper plating additive to be beneficial to obtaining a bright copper coating.
Preferably, the use method of the cyanide-free electroplating brass liquid comprises the following steps:
s1, preparing an electroplating solution: adding pyrophosphate into deionized water, stirring and fully dissolving; dissolving copper sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dripping pH regulator until the solution is clear to obtain solution A; dissolving zinc sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dropwise adding a pH regulator until the solution is clear to obtain a solution B; adding an auxiliary complexing agent, a conductive agent, a main brightening agent, an auxiliary brightening agent and methyl glucitol polyether into deionized water for dissolving to obtain a solution C; uniformly mixing the solution A, B, C, adding a pH regulator, regulating the pH value to 8.5-9, fully stirring, uniformly mixing, and fixing the volume to obtain electroplating solution;
s2, electroplating of the plated part: selecting an activated workpiece to be plated as a cathode material and a brass plate as an anode material, adding a plating solution, wherein the plating temperature is 35-45 ℃, the plating time is 5-20 min, and the current density is 3-5A/dm2The brass plating layer is prepared by direct current electrodeposition under the condition of (1).
Preferably, in the method for using the cyanide-free electroplating brass liquid, the S1 cathode material is one of bright nickel-plated carbon steel, cast iron, aluminum alloy and zinc die casting.
Pyrophosphate is a cyanide-free brass electroplating system developed earlier, which can overcome the problems of environmental pollution and harm to human health caused by cyanide-containing electroplating, but in the practical operation process, when pyrophosphate is used as a complexing agent to electroplate copper-zinc alloy, the color of a plating layer is difficult to control, pinholes or coarse metal particles are easy to appear on the surface of the plating layer, in addition, in the electroplating process, the range of the deposited current density is narrow, and when the current density is too high or too low, the plating layer has poor effect. Therefore, in order to overcome these problems, the present inventors have conducted extensive experiments and found that the addition of a primary brightener containing a mercapto group, a secondary brightener containing a quaternary ammonium ion, and methyl glucitol polyether to a brass plating liquid system can improve the problems of difficulty in controlling the color of a plating layer and a narrow range of deposition current density.
The methyl glucitol polyether is a polyether compound prepared from glucose and methanol, has good water retention capacity due to more ether bonds, and can be used as an emollient and a humectant in daily chemicals. The reason that the methyl glucitol polyether is added into the electroplating solution to improve the coating color and luster and is not easy to control and the deposition current density range is narrower is probably that the methyl glucitol polyether serving as a polyether compound can effectively improve the overvoltage of the coating, refine the coating crystal grains, expand the bright current density range and improve the dispersion capacity of a system. When the brightening agent is used together with a main brightening agent containing sulfydryl and an auxiliary brightening agent containing quaternary ammonium ions, the main brightening agent, the auxiliary brightening agent containing sulfydryl and the auxiliary brightening agent are cooperated to inhibit preferential precipitation of copper, and the current density range of electrodeposition is enlarged.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cyanide-free electroplating brass liquid provided by the invention is added with the brightening agent and the methyl glucitol polyether, so that an electroplating brass coating with uniform color and good brightness can be obtained.
(2) The main brightener, the auxiliary brightener and the methyl glucitol polyether have synergistic effect, so that the upper limit and the lower limit of the deposition current density of electroplating are improved, the stability of brass electroplating can be enhanced, and the electroplating efficiency is improved.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1-5 formulation of a cyanide-free electroplated brass solution
Examples 1 to 5, a formulation of a cyanide-free electroplated brass liquid, using deionized water as a solvent, the components of which are shown in the following table:
example 6, method of using a cyanide-free electroplated brass liquid comprising the steps of:
s1, preparing an electroplating solution: adding pyrophosphate into deionized water, stirring and fully dissolving; dissolving copper sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dripping pH regulator until the solution is clear to obtain solution A; dissolving zinc sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dropwise adding a pH regulator until the solution is clear to obtain a solution B; adding an auxiliary complexing agent, a conductive agent, a brightening agent and methyl glucitol polyether into deionized water for dissolving to obtain a solution C; uniformly mixing the solution A, B, C, adding a pH regulator, regulating the pH value to 12.5, fully stirring, uniformly mixing, and fixing the volume to obtain electroplating solution;
s2, electroplating of the plated part: selecting an activated workpiece to be plated as a cathode material and a brass plate as an anode material, adding a plating solution, wherein the plating temperature is 40 ℃, the plating time is 10min, and the current density is 2A/dm2Preparing a brass plating layer by direct current electrodeposition under the condition of (1);
s3, post-treatment of the plated part: and (3) after the electroplating is finished, cleaning the plated part with water, passivating by a potassium dichromate method, washing with clear water at 80-100 ℃, drying, and coating a protective paint to obtain the metal material plated part with the surface plated with the copper-zinc alloy.
Comparative example 1 formula of cyanide-free electroplated brass liquid and use method thereof
The formulation of the cyanide-free electroplating brass liquid refers to example 1, and the using method refers to example 6, except that the components do not contain a main brightener and an auxiliary brightener, and other components and experimental parameters are the same.
Comparative example 2 formula of cyanide-free electroplated brass liquid and use method thereof
The formulation of the cyanide-free electroplating brass liquid refers to example 1, and the using method refers to example 6, except that the components do not contain methyl glucitol polyether, and other components and experimental parameters are the same.
Comparative example 3 formula of cyanide-free electroplated brass liquid and use method thereof
The formulation of the cyanide-free electroplated brass liquid refers to example 1, and the application method refers to example 6, except that the components do not contain auxiliary brightener and methyl glucitol polyether, and other components and experimental parameters are the same.
Test example I, observation of coating brightness and color
The brass plated parts prepared by the methods of examples 1 to 5 and comparative examples 1 to 3 were observed for brightness and color by visual observation, and the appearance of the plated layer was observed under an SEM electron microscope, and the test results are shown in table 1.
TABLE 1 test results of coating brightness and color
The experimental results in table 1 show that the plating layers obtained in examples 1 to 5 have good brightness, uniform color, dense plating layer and no corrosion, and compared with comparative examples 1 to 3, the plating effect is good, which indicates that the methyl glucitol polyether and the brightener cooperate with each other to improve the quality of the plating layer.
Test example two, Upper and lower limits test of plating bath deposition Current Density
The current density range of the deposition is calculated by adopting a Hall cell experimental method, taking 230mL of electroplating brass liquid in a 250mL Hall cell, taking a copper sheet which is plated with bright nickel and has the thickness of 80mm multiplied by 60mm multiplied by 0.2mm as a cathode, adjusting the current, taking the time when the plating layer has coarse grains/is burnt fast as the highest current, and the time when the plating layer has golden color band disappeared as the lowest current according to the following formula.
Jk=I(5.1-5.241gl)
In the formula: jk-deposition Current Density (A/dm) at a certain position of cathode2)
I-Current (A) used in the Experimental procedure
l-distance (cm) from a certain position on the cathode to the proximal end
TABLE 2 deposition Current Density Range of electroplating baths
Test group Upper limit of current density (A/dm)2) Lower limit of Current Density (A/dm)2)
Example 1 12.84 1.14
Example 2 13.26 0.98
Example 3 13.51 0.94
Example 4 13.16 0.92
Example 5 12.94 1.08
Comparative example 1 10.95 1.52
Comparative example 2 5.44 2.52
Comparative example 3 5.19 2.64
As can be seen from Table 1, the range of the deposition current density of examples 1 to 5 is significantly larger than that of comparative examples 1 to 3, and the range of the current density of example 3 is 0.94 to 13.5A/dm, which is the largest range2It is shown that the addition of the main brightener, the auxiliary brightener and the methyl glucitol polyether is beneficial to increasing the deposition density range of the copper electroplating solution. In the electroplating operation, the upper limit of the deposition current density is increased, which is favorable for improving the plating speed of electroplating, obtaining a more compact electroplated layer and improving the electroplating efficiency, and in addition, the increase of the range of the deposition current density is also favorable for stably electroplating brass.
It will be appreciated by those skilled in the art that the above embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (9)

1. The cyanide-free electroplating brass liquid is characterized in that deionized water is used as a solvent, and the cyanide-free electroplating brass liquid comprises the following components: 15-35 g/L copper sulfate, 8-20 g/L zinc sulfate, 120-200 g/L pyrophosphate, 1-3 g/L auxiliary complexing agent 10-20 g/L, pH regulator, 20-40 g/L conductive agent, 0.01-0.02 g/L main brightener, 0.001-0.1 g/L auxiliary brightener and 0.1-1 g/L methyl glucitol polyether.
2. The cyanide-free electroplated brass liquid of claim 1, wherein deionized water is used as a solvent, comprising the following components: 20-25 g/L of copper sulfate, 12-15 g/L of zinc sulfate, 140-160 g/L of pyrophosphate, 15-20 g/L, pH g/L of auxiliary complexing agent regulator 1.8-2.2 g/L, 30-35 g/L of conductive agent, 0.05-0.01 g/L of main brightener, 0.005-0.1 g/L of auxiliary brightener and 0.3-0.5 g/L of methyl glucitol polyether.
3. The cyanide-free electroplated brass liquid of claim 1, wherein the auxiliary complexing agent is at least one of potassium citrate, sodium citrate, potassium oxalate and sodium oxalate.
4. The cyanide-free electroplated brass fluid of claim 1, wherein the pH adjusting agent comprises at least one of sodium hydroxide and potassium hydroxide.
5. The cyanide-free electrolytic brass plating solution according to claim 1, wherein the conductive agent comprises at least one of potassium chloride, sodium chloride, potassium carbonate, dipotassium hydrogen phosphate and potassium nitrate.
6. The cyanide-free electroplated brass fluid of claim 1, wherein the primary brightener is at least one of sodium mercaptoimidazolepropanesulfonate, sodium 3- (benzothiazole-2-mercapto) propanesulfonate, and sodium 2-mercapto-5-benzimidazolesulfonate.
7. The cyanide-free electroplated brass fluid of claim 1, wherein the secondary brightener is 1-benzylpyridinium-3-carboxylate.
8. The use method of the cyanide-free electroplated brass liquid as claimed in any one of claims 1 to 7, comprising the following steps:
s1, preparing an electroplating solution: adding pyrophosphate into deionized water, stirring and fully dissolving; dissolving copper sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dripping pH regulator until the solution is clear to obtain solution A; dissolving zinc sulfate in deionized water, adding 1/2 the prepared pyrophosphate solution, and dropwise adding a pH regulator until the solution is clear to obtain a solution B; adding an auxiliary complexing agent, a conductive agent, a main brightening agent, an auxiliary brightening agent and methyl glucitol polyether into deionized water for dissolving to obtain a solution C; uniformly mixing the solution A, B, C, adding a pH regulator, regulating the pH value to 8.5-9, fully stirring, uniformly mixing, and fixing the volume to obtain electroplating solution;
s2, electroplating of the plated part: selecting an activated workpiece to be plated as a cathode material and a brass plate as an anode material, adding a plating solution, wherein the plating temperature is 35-45 ℃, the plating time is 5-20 min, and the current density is 3-5A/dm2The brass plating layer is prepared by direct current electrodeposition under the condition of (1).
9. The method of claim 8, wherein the cathode material of S1 is one of bright nickel plated carbon steel, cast iron, aluminum alloy, and zinc die casting.
CN201911001769.4A 2019-10-21 2019-10-21 Cyanide-free electroplating brass liquid and use method thereof Pending CN110592626A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112899666A (en) * 2021-01-19 2021-06-04 广州三孚新材料科技股份有限公司 Chemical copper plating brightener and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1295985A1 (en) * 2001-09-20 2003-03-26 Sumitomo Rubber Industries Ltd. Method for making coated metallic cord
CN101270492A (en) * 2007-03-21 2008-09-24 来明工业(厦门)有限公司 Stannum copper alloy coating, plating solution prescription and electroplating method
CN105829583A (en) * 2013-12-17 2016-08-03 优美科电镀技术有限公司 Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1295985A1 (en) * 2001-09-20 2003-03-26 Sumitomo Rubber Industries Ltd. Method for making coated metallic cord
CN101270492A (en) * 2007-03-21 2008-09-24 来明工业(厦门)有限公司 Stannum copper alloy coating, plating solution prescription and electroplating method
CN105829583A (en) * 2013-12-17 2016-08-03 优美科电镀技术有限公司 Deposition of copper-tin and copper-tin-zinc alloys from an electrolyte

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112899666A (en) * 2021-01-19 2021-06-04 广州三孚新材料科技股份有限公司 Chemical copper plating brightener and preparation method thereof
CN112899666B (en) * 2021-01-19 2022-06-14 广州三孚新材料科技股份有限公司 Chemical copper plating brightener and preparation method thereof

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