CN1896307A - Copper-alloy chemical nickeling process - Google Patents
Copper-alloy chemical nickeling process Download PDFInfo
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- CN1896307A CN1896307A CN 200510035822 CN200510035822A CN1896307A CN 1896307 A CN1896307 A CN 1896307A CN 200510035822 CN200510035822 CN 200510035822 CN 200510035822 A CN200510035822 A CN 200510035822A CN 1896307 A CN1896307 A CN 1896307A
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Abstract
The present invention is a chemical nickel plating technology of copper alloy including: acid pickling of the alloy surface to remove the grease, pre-electroplating, and electroplating by a chemical nickel plating process. The present invention has simplified technology, convenient maintenance and low cost. It also enables chemical nickel plating to process on the copper alloy surface. The bath of pre-electroplating and chemical nickel plating features in low operation temperature and neutral pH. This technology also bypasses the activation process, avoids the influence of the former technology on the chemical nickel bath and elongates the lifespan of the bath.
Description
Technical Field
The invention relates to the field of electroplating, in particular to a copper alloy chemical nickel plating process.
Background
Electroless plating is a process that produces metal deposits by a controlled redox reaction under the catalytic action of the metal. It is also known as autocatalytic plating or electroless plating.
The following conditions should be met for realizing electroless plating: (1) the reducing agent in the solution is oxidized at a potential substantially lower than the potential at which the metal ions are reduced, so that the metal may be deposited on the substrate; (2) the prepared solution does not generate spontaneous decomposition, and when the prepared solution is contacted with a catalytic surface, a metal deposition process occurs; (3) when the pH and the temperature of the solution are adjusted, the reduction speed of the metal can be controlled, namely the plating speed can be adjusted; (4) the metal precipitated by reduction should have catalytic activity, so that the coating can be thickened; (5) the reaction products do not interfere with the proper operation of the plating process, i.e., the solution has a sufficient life.
The chemical plating solution comprises metal salt, reducing agent, complexing agent, buffering agent, pH regulator, stabilizer, accelerator, wetting agent, brightener and the like. Compared with electroplating, chemical plating has the characteristics of uniform plating thickness, few pinholes, no need of direct-current power supply equipment, capability of depositing on a non-conductor, certain special properties and the like. But the cost is higher than that of electroplating, and the method is mainly used for special occasions which are not suitable for electroplating.
Electroless nickel is the most widely used electroless nickel plating solution, and the electroless nickel plating solution usually uses hypophosphite as a reducing agent. The reaction process is as follows:
The coating is characterized in that: (1) the obtained plating layer is a nickel-phosphorus alloy containing a certain amount of phosphorus, and the phosphorus content of the plating layer is changed between 3 percent and 14 percent along with the difference of solution components and operation conditions; (2) the coating is amorphous and has a layered structure, and is subjected to heat treatment with Ni3The layered structure of the P gradually disappears after the P is crystallized, and when the phosphorus content is higher than 8 percent, the plating layer is nonmagnetic; when the phosphorus content is lower than 8%, the magnetic property of the alloy is also greatly different from that of the electroplated nickel layer; (3) the corrosion resistance is high, particularly when the phosphorus content is high, and the corrosion resistance is much higher than that of electroplated nickel in many corrosive mediums; (4) the hardness is high, the microhardness of the plating layer is approximately equal to 500-600HV, and is much higher than that of an electroplated nickel layer, after the plating layer is subjected to heat treatment at 400 ℃, the hardness can reach more than 1000HV, the plating layer can be used for replacing hard chromium plating, and the toughness is poorer than that of the electroplated nickel layer; (5) easy to braze, but the welding performance is poorer than that of a nickel plating layer; (6) certain electroless nickel coatings have an appearance similar to stainless steel and are more aesthetically pleasing than yellowish nickel coatings.
The chemical nickel-phosphorus plating layer is mainly used as a corrosion-resistant plating layer of chemical equipment, a wear-resistant plating layer of complex mechanical parts, a brazing plating layer of electronic components, an electromagnetic shielding layer of electronic instruments, metallization of nonconductors and the like.
Chemical nickel plating is carried out on different base metals, and the chemical nickel plating can be divided into the following types according to different catalytic activities of the base metals to the chemical nickel plating:
1. metals of high catalytic activity
Such as common steel, nickel, cobalt, platinum, palladium and the like, the chemical nickel plating can be directly carried out after the pretreatment before the common electroplating.
2. Catalytically active metals with surface susceptible to oxidation
Such as stainless steel, aluminum, magnesium, titanium, tungsten, molybdenum, etc., which are activated appropriately before being electroless plated.
3. Non-catalytically active metals
Such as copper, silver, gold, etc., which require a triggering or catalytic treatment before electroless nickel plating can be performed.
(1) And (3) galvanic couple triggering: at the beginning of electroless nickel plating, it is brought into contact with a metal such as steel, aluminum, etc., and nickel is deposited due to the triggering action of the galvanic couple.
(2) Triggering by an external power supply: at the beginning of chemical nickel plating, the part is connected with the cathode, and after a thin layer of nickel is plated by an external power supply, the chemical nickel plating process can be normally carried out.
(3) Palladium chloride immersion activation: after the part is soaked in a palladium chloride solution, a layer of palladium with high catalytic performance is arranged on the surface of the part, so that chemical palladium nickel can be smoothly carried out. However, since the activating solution has an influence on the electroless plating solution, the solution is thoroughly washed after immersion to prevent palladium chloride from entering the plating solution to cause natural decomposition of the plating solution.
Copper and its alloy are used as non-catalytic active metal, because the electrode potential is positive, it can not be directly used for chemical nickel plating, and it belongs to the base material difficult for chemical nickel plating, and it can be used for chemical nickel plating after trigger or catalytic treatment. The pretreatment process generally requires activation, for example, after dipping in a palladium chloride solution, a layer of noble metal palladium with high catalytic activity is deposited on the surface of the part, so that the chemical nickel plating can be smoothly carried out. However, the process is high in cost, the chemical plating process is complicated and difficult to maintain, and the activating solution has an influence on the chemical plating solution, so that the chemical plating solution is thoroughly washed after immersion, the palladium chloride is prevented from entering the plating solution to cause natural decomposition of the plating solution, and the service cycle of the chemical nickel plating solution is shortened. The nickel preplating activation method can effectively prevent harmful metal ions in brass from dissolving out to pollute the chemical plating solution, is very favorable for ensuring the bonding strength of the plating layer, but has poor dispersion capability due to the influence of electric field distribution on the electroplating, is difficult to obtain a nickel preplating layer on the inner surfaces of workpieces with complex shapes, such as deep holes and blind holes, and the typical nickel preplating pretreatment process of the prior copper and copper alloy is still complex and comprises the following steps: chemical degreasing → hot water cleaning → cold water cleaning → electrolytic cleaning → secondary degreasing → hot water cleaning → cold water cleaning → electrolytic cleaning → nickel preplating activation → cold water cleaning → deionized water cleaning, so the production time is long, the efficiency is low, and the production cost and the equipment cost are high.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a copper alloy chemical nickel plating process, which simplifies the process and prolongs the service life of the plating solution, and the plating solution has low operation temperature and nearly neutral pH.
The purpose of the invention is realized as follows: a copper alloy chemical nickel plating process is characterized by comprising the following steps:
-degreasing and cleaning;
-weak acid washing;
-pre-plating;
-electroless nickel plating: chemical nickel plating is carried out by using a plating solution containing the following components, wherein the components of the plating solution comprise 20-30g/L of soluble nickel salt, 15-20g/L of complexing agent, 20-30g/L of hypophosphite reducing agent and 2-5mg/L, pH of stabilizing agent, the pH value of the plating solution is adjusted to 7.0-9.5, and the operation conditions are as follows: stirring, and controlling the temperature of the plating solution at 50-55 ℃;
-post-treatment.
The operation conditions of the pre-plating step are as follows: the temperature is 40-55 deg.C, voltage is 2-4V, and current density is 0.2-0.4A/dm2And the time is 1-2 minutes.
The process has the advantages of simple process, simple maintenance, removal of the activation process, cost saving, low operation temperature of the plating solution and nearly neutral pH, avoids the influence of the prior process on the chemical nickel plating solution due to no activation process, and prolongs the service cycle of the plating solution.
Detailed Description
The invention relates to a copper alloy chemical nickel plating process, which comprises the following steps: degreasing and cleaning; weak acid washing; pre-electroplating; chemical nickel plating; and (5) post-treatment.
Degreasing and cleaning are to remove oil stains on the surface of the product by a chemical method, such as degreasing by hot alkali liquor or degreasing by a surfactant.
Weak acid washing, and removing rust by hydrochloric acid solution.
Pre-electroplating, wherein the operation conditions are as follows: the temperature is 40-55 deg.C, voltage is 2-4V, and current density is 0.2-0.4A/dm2The time is 1-2 minutes, after a thin layer of nickel is plated by an external power supply, the chemical nickel plating process can be normally carried out.
Chemical nickel plating: the plating solution comprises water, soluble nickel salt, a complexing agent, a hypophosphite reducing agent, a stabilizing agent, a pH regulator and the like. Soluble nickel salts generally employ nickel sulfate which is widely available, less costly, and more soluble, while any other nickel salt meeting the solubility criteria is suitable. The concentration of soluble nickel salt in the bath may be in the range of 20-30 g/L. The reducing agent is preferably a hypophosphite, in particular sodium hypophosphite. The concentration of the reducing agent in the plating solution may be in the range of 20-30 g/L. The pH regulator is alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide, or compound containing ammonia water and ammonium ion, and is added into the plating solution to maintain pH value of 7.0-9.5. The complexing agent is selected from various organic acids or organic acid salts, such as citric acid, lactic acid, tartaric acid, succinic acid, malic acid, gluconic acid, etc., or salts of the above organic acids. The complexing agent concentration in the plating solution can be in the range of 15-20 g/L. The stabilizer is used for stabilizing the components of the plating solution, preferably potassium iodate, and the concentration of the stabilizer in the plating solution is 2-5 mg/L. The deposition rate gradually increases with increasing nickel salt and hypophosphite concentration and then tends to stabilize or slightly decrease, but the solution stability decreases at this time. The two chemicals are main consumption components of chemical nickel plating and need to be supplemented frequently. The two should be added separately, and the solution temperature should be lower and the stirring should be good. If the water can be supplemented by a metering pump of a watchband of an automatic control instrument, the water is most ideal. The operation process of the plating solution adopts air stirring, the temperature is 50-55 ℃, and the pH value of the plating solution is maintained between 7.0-9.5. The electroless nickel reaction is affected by the diffusion process. Stirring the chemical nickel plating solution is beneficial to improving the transfer speed of reactants to the surface of a workpiece, and is also beneficial to the separation of reaction products, so that plating leakage and pinholes can be prevented, the appearance quality of a plating layer can be improved, local overheating can be prevented, and the stability of the plating solution is facilitated. Essentially, agitation changes the chemical composition and pH within the diffusion layer at the workpiece/solution interface, and therefore, the effect of agitation is important. When direct heating is performed by steam or electric heaters, the solution must have an air agitation or continuous circulation system to allow the heated solution to spread out quickly. When the pH value of the plating solution is low, the effect of improving the plating speed by air stirring is more obvious; ultrasonic agitation at high pH is beneficial to increasing the plating speed. Air agitation is used in the present invention.
And (3) post-treatment: baking and heat treatment for improving the adhesion property of the coating.
The following examples are further illustrative, but the present invention is not limited to the following examples.
Firstly, degreasing and cleaning are carried out, wherein alkali liquor components (containing 15-20g/L of sodium hydroxide, 15-30g/L of sodium carbonate, 15-30g/L of sodium phosphate and 2g/L of sodium dodecyl benzene sulfonate) are cleaned at the temperature of 20-60 ℃ for 0.5-1 minute.
Then weak acid washing is carried out, and the solution is washed by 100-200mL/L hydrochloric acid solution for 0.5-2 minutes at room temperature.
Then pre-plating is carried out, the components of the pre-plating solution are the same as those of the chemical nickel plating solution, and the operation conditions are as follows: the temperature is 40-55 deg.C, the voltage is 2-4V, and the current density is 0.2-0.4A/dm2And the time is 1-2 minutes.
And then carrying out chemical nickel plating. The process specification is as follows:
and finally, carrying out post-treatment: the baking temperature is 60-70 deg.C, and the baking time is 30-60 min.
The performance of the plated layer after plating was tested as follows:
| item | Test results |
| Thickness of coating | 3-5 microns |
| Phosphorus content of the coating | 5％-8％ |
| Salt spray test | And (4) testing standard: 50 +/-1 g/L of salt solution; the pH value at 35 ℃ should be Keeping in the range of 6.5-7.2; the salt spray sedimentation rate is 1.0-2.0ml/h (within a horizontal collection area of 80cm 2); effective test in test chamber The temperature in the space is 35 +/-2 ℃; spraying in specified test period The fog must not be interrupted. After the test piece is taken out from the salt spray corrosion box, the application Washing with tap water at a temperature of not more than 38 deg.CWashing, and checking after drying. After 24 hours of testing, no peeling, no cracking, no wrinkling, no lifting Bubble phenomenon. |
| Adhesion Properties | Baking at 150 deg.C for 10 min, without Bubbles, no wrinkles. |
Claims (10)
1. A copper alloy chemical nickel plating process is characterized by comprising the following steps:
-degreasing and cleaning;
-weak acid washing;
-pre-plating;
-electroless nickel plating: chemical nickel plating is carried out by using a plating solution containing the following components, wherein the components of the plating solution comprise 20-30g/L of soluble nickel salt, 15-20g/L of complexing agent, 20-30g/L of hypophosphite reducing agent and 2-5mg/L, pH of stabilizing agent, the pH value of the plating solution is adjusted to 7.0-9.5, and the operation conditions are as follows: stirring, and controlling the temperature of the plating solution at 50-55 ℃;
-post-treatment.
2. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the pre-electroplating step comprises the following operating conditions: the temperature is 40-55 ℃, the voltage is 2-4V, the current density is 0.2-0.4A/dm2, and the time is 1-2 minutes.
3. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the components of the pre-plating solution in the pre-plating step are the same as those of the chemical nickel plating solution.
4. A process of electroless nickel plating of copper alloys as claimedin claim 1 wherein: the complexing agent in the chemical nickel plating solution is sodium citrate.
5. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the hypophosphite reducing agent in the chemical nickel plating solution is sodium hypophosphite.
6. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the stabilizer in the chemical nickel plating solution is potassium iodate.
7. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the pH regulator in the chemical nickel plating solution is ammonia water or alkali metal hydroxide.
8. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: and stirring in the operation condition of the chemical nickel plating step adopts air stirring.
9. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the chemical nickel plating time is 4-10 minutes.
10. A process of electroless nickel plating of copper alloys as claimed in claim 1 wherein: the post-treatment operation process is that the baking temperature is 60-70 ℃ and the time is 30-60 min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100358224A CN100476026C (en) | 2005-07-11 | 2005-07-11 | Copper-alloy chemical nickeling process |
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| CNB2005100358224A CN100476026C (en) | 2005-07-11 | 2005-07-11 | Copper-alloy chemical nickeling process |
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| CN1896307A true CN1896307A (en) | 2007-01-17 |
| CN100476026C CN100476026C (en) | 2009-04-08 |
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| CN103484841A (en) * | 2013-10-10 | 2014-01-01 | 青岛黎马敦包装有限公司 | Production technology of fine bronzing plate with high precision and hardness |
| CN103882492A (en) * | 2014-02-24 | 2014-06-25 | 哈尔滨工程大学 | Chemical plating posttreatment method of metallic matrix |
| CN104372314A (en) * | 2013-08-12 | 2015-02-25 | 国家电网公司 | Condenser brass tube chemical nickel plating method |
| CN109066148A (en) * | 2018-07-25 | 2018-12-21 | 深圳市爱默斯科技有限公司 | Welding female and its electroplating technology |
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| CN115161736A (en) * | 2022-07-28 | 2022-10-11 | 清远敏惠汽车零部件有限公司 | Plastic autocatalysis electroplating process |
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| CN104372314A (en) * | 2013-08-12 | 2015-02-25 | 国家电网公司 | Condenser brass tube chemical nickel plating method |
| CN103484841A (en) * | 2013-10-10 | 2014-01-01 | 青岛黎马敦包装有限公司 | Production technology of fine bronzing plate with high precision and hardness |
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| CN103882492A (en) * | 2014-02-24 | 2014-06-25 | 哈尔滨工程大学 | Chemical plating posttreatment method of metallic matrix |
| CN103882492B (en) * | 2014-02-24 | 2016-08-24 | 哈尔滨工程大学 | Metallic matrix chemical plating pre-treating method |
| CN109066148A (en) * | 2018-07-25 | 2018-12-21 | 深圳市爱默斯科技有限公司 | Welding female and its electroplating technology |
| CN112647103A (en) * | 2020-12-18 | 2021-04-13 | 成都宏明双新科技股份有限公司 | Iron part broken section salt spray test lifting method |
| CN115161736A (en) * | 2022-07-28 | 2022-10-11 | 清远敏惠汽车零部件有限公司 | Plastic autocatalysis electroplating process |
| CN116805655A (en) * | 2023-07-26 | 2023-09-26 | 环晟光伏(江苏)有限公司 | TOPCO battery preparation method and TOPCO battery prepared by same |
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|---|---|
| CN100476026C (en) | 2009-04-08 |
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