CN100476026C - Copper-alloy chemical nickeling process - Google Patents
Copper-alloy chemical nickeling process Download PDFInfo
- Publication number
- CN100476026C CN100476026C CNB2005100358224A CN200510035822A CN100476026C CN 100476026 C CN100476026 C CN 100476026C CN B2005100358224 A CNB2005100358224 A CN B2005100358224A CN 200510035822 A CN200510035822 A CN 200510035822A CN 100476026 C CN100476026 C CN 100476026C
- Authority
- CN
- China
- Prior art keywords
- plating
- copper
- nickel
- chemical
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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 present invention relates to field of electroplating, particularly a kind of copper-alloy chemical nickeling process.
Background technology
Electroless plating is under the katalysis of metal, produces the process of metal deposition by controllable redox reaction.It is also referred to as autocatalytic plating or electroless plating.
Realize that electroless plating should possess following condition: the oxidized current potential of reductive agent will significantly be lower than the current potential that metal ion is reduced in (1) solution, so that metal might be deposited out on base material; (2) solution for preparing does not produce spontaneous decomposition, when contacting with catalytic surface, metal deposition process takes place; (3) when the pH of regulator solution, temperature, the reduction rate of metal can be controlled, promptly plating speed can be regulated; (4) metal that is restored should have catalytic activity, and coating just can thicken like this; (5) resultant of reaction does not hinder normally carrying out of plating process, and ie in solution has enough work-ing life.
The composition of chemical plating solution comprises metal-salt, reductive agent, complexing agent, buffer reagent, pH regulator agent, stablizer, accelerator, wetting agent and brightening agent etc.Compare with plating, electroless plating has that thickness of coating is even, pin hole is few, do not need DC power supply device, can deposit and have characteristics such as some property on non-conductor.But cost is higher than electroplating, and is mainly used in and is unsuitable for galvanized special occasions.
Most widely used in the electroless plating is chemical nickel plating, and chemical nickel-plating solution is normally made reductive agent with hypophosphite.Its reaction process is:
Ni
2++H
2PO
2 -+H
2O——→HPO
3 2-+3H
++Ni
H
2PO
2 -+ H---→ P+H
2O+OH
-(section H
2PO
2 -Being reduced into phosphorus by hydrogen atom is mixed in the coating)
H
2PO
2 -+ H
2O---→ H
++ HPO
3 2-+ H
2↑ (evolving hydrogen reaction)
The characteristics of this class coating are: (1) gained coating is the nickel-phosphorus alloy that contains some amount phosphorus, and its phosphorus content changes between 3%-14% with the difference of solution composition and operational condition; (2) coating is amorphous laminate structure, when heat-treating, along with Ni
3The crystallization of P, its laminate structure fades away, and phosphorus content is higher than at 8% o'clock, and coating is non magnetic; Phosphorus content is lower than at 8% o'clock, and its magnetic property also has very big-difference with electroless nickel layer; (3) corrosion stability height, particularly when phosphorus content is higher, all much anti-corrosion in many erosion media than electronickelling; (4) hardness height, the microhardness ≈ 500-600HV of this coating, more much higher than electroless nickel layer, after 400 ℃ of thermal treatment, its hardness can reach more than the 1000HV, can be used to replace hard chrome plating, and toughness is than electroless nickel layer difference; (5) be easy to soldering, but the melting welding performance is than nickel coating difference; (6) outward appearance of some chemical Ni-plating layer is similar to stainless steel, and yellowish nickel coating is attractive in appearance than being with.
The chemical nickel phosphorus plating layer is mainly as the electro-magnetic screen layer of the soldering coating of the scuff-resistant coating of the coating against corrosion of chemical industry equipment, complex mechanical, electronic devices and components, electronic machine and idioelectric metallization etc.
Chemical nickel plating on the different matrix metal can be divided into following a few class by matrix metal to chemical nickel plating catalytic activity difference:
1, the metal of high catalytic activity
As common iron and steel, nickel, cobalt, platinum, palladium etc., these metals can direct chemical nickel plating after the pre-treatment before general the plating.
2, catalytic activity is arranged but the easy metal of oxidation in surface
As stainless steel, aluminium, magnesium, titanium, tungsten, molybdenum etc., this metalloid will carry out just carrying out chemical nickel plating after the suitable activation treatment.
3, the active metal of on-catalytic
As copper, silver, gold etc., they need do just can carry out chemical nickel plating after triggering or the catalytic treatment.
(1) galvanic couple triggers: initial at chemical nickel plating makes metallic contact such as itself and steel, aluminium, owing to the trigger action of galvanic couple is come out nickel deposition.
(2) external power triggers: initial at chemical nickel plating, and make part connect negative electrode, rely on additional power source and after the skim nickel that plates, nickel process just can normally be carried out.
(3) soak the Palladous chloride activation: behind the dipping, piece surface has the high palladium of one deck catalytic, and chemical palladium nickel can be carried out smoothly in palladium chloride solution.But because activation solution is influential for chemical plating fluid, therefore to thoroughly wash behind the dipping, cause the natural decomposition of plating bath to prevent Palladous chloride from entering plating bath.
Copper and alloy thereof are as the on-catalytic reactive metal, because electropotential for just, can not directly carry out chemical nickel plating, the difficult plating of genus chemical nickel plating base material needs to do just can carry out chemical nickel plating after triggering or the catalytic treatment.Generally all must activate in its pre-treating technology, for example in palladium chloride solution, behind the dipping, on piece surface, deposit the high precious metal palladium of one deck catalytic activity, chemical nickel plating can be carried out smoothly.But this process cost height, and make chemical plating technology complicated, not easy care, activation solution is influential for chemical plating fluid simultaneously, therefore to thoroughly wash behind the dipping, cause the natural decomposition of plating bath to prevent Palladous chloride from entering plating bath, shorten the life cycle of chemical nickel-plating liquid.Though and employing nickel preplating activation method can very prevent harmful metal ion stripping in the brass and pollute chemical plating fluid effectively, for guaranteeing that coat binding strength is highly beneficial, but influenced by electric field distribution owing to electroplate, dispersive ability is poor, for complex-shaped workpiece, as deep hole, the internal surface of blind hole is difficult to obtain pre-nickel plating, and at present copper and the typical nickel preplating pre-treating technology of copper alloy are still complicated, include: electrochemical deoiling → hot water cleaning → cold water cleaning → electrolytic cleaning → secondary oil removing → hot water cleaning → cold water cleaning → electrolytic cleaning → processing steps such as nickel preplating activation → cold water cleaning → deionization washing, therefore the production time is long, efficient is lower, and production cost and equipment cost are higher.
Summary of the invention
For addressing the above problem, the purpose of this invention is to provide a kind of copper-alloy chemical nickeling process, it has simplified technological process, and has prolonged the life cycle of plating bath, and the plating bath service temperature is low, and pH is near neutral.
The object of the present invention is achieved like this: a kind of copper-alloy chemical nickeling process is characterized in that may further comprise the steps:
-cleaning by degreasing;
-weak acid is washed;
-pre-the plating;
-chemical nickel plating: carry out chemical nickel plating with the plating bath that contains following component, bath composition comprises that it is 7.0-9.5 that soluble nickel salt 20-30g/L, complexing agent 15-20g/L, hypophosphite reductive agent 20-30g/L, stablizer 2-5mg/L, pH regulator agent transfer to bath pH value, operational condition is: stir, bath temperature is controlled at 50-55 ℃;
-aftertreatment.
Above-mentioned pre-plating step operational condition is: temperature is 40-55 ℃, voltage 2-4V, current density 0.2-0.4A/dm
2, time 1-2 minute.
Technological process of the present invention is oversimplified, safeguard simple, removed reactivation process, provide cost savings, chemical nickel plating can be carried out at copper alloy surface, and the plating bath service temperature is low, pH is near neutral, this technology has been avoided the influence of former technology for chemical nickel-plating liquid owing to there is not reactivation process, plating bath life cycle lengthening.
Embodiment
The present invention is a kind of copper-alloy chemical nickeling process, may further comprise the steps: cleaning by degreasing; Weak acid is washed; The pre-plating; Chemical nickel plating; Aftertreatment.
Cleaning by degreasing is to slough the product surface greasy dirt with chemical process, for example utilizes the heat alkali liquid degreasing or utilizes the tensio-active agent degreasing.
Weak acid is washed, and eliminates rust with hydrochloric acid soln.
The pre-plating, its operational condition is: temperature is bath temperature 40-55 ℃, voltage 2-4V, current density 0.2-0.4A/dm
2, time 1-2 minute, rely on additional power source and plate after the skim nickel, nickel process just can normally be carried out.
Chemical nickel plating: plating bath includes water, soluble nickel salt, complexing agent, hypophosphite reductive agent, stablizer, pH regulator agent etc.Soluble nickel salt adopts generally that the source is wide, cost is lower, solubleness single nickel salt preferably, and other any nickel salt that meets solubility criteria all is fit to.The soluble nickel salt concn can be in the 20-30g/L scope in plating bath.Reductive agent preferred hypophosphite, particularly inferior sodium phosphate.Reductant concentration can be in the 20-30g/L scope in plating bath.Alkali metal hydroxide is adopted in the pH regulator agent, as sodium hydroxide, potassium hydroxide, or the compound that contains ammoniacal liquor, ammonium ion all can, the pH value that is added into plating bath maintains between the 7.0-9.5.The selection of complexing agent is a lot, comprises various organic acids or organic acid salt, as citric acid, lactic acid, tartrate, succsinic acid, oxysuccinic acid, gluconic acid etc., or above organic acid salt.Complexing agent concentration can be in the 15-20g/L scope in plating bath.Stablizer is used for stablizing bath composition, preferred Potassium Iodate, and concentration is 2-5mg/L in plating bath.Along with the increase of nickel salt and ortho phosphorous acid salt concn, sedimentation velocity improves gradually, then tended towards stability or reduction arranged slightly, but stability of solution descended this moment.These two kinds of medicines are main consumption compositions of chemical nickel plating, often replenish.Both should dissolve adding respectively when replenishing, add fashionable solution temperature lower for well, and good stirring to be arranged.If it is can add, ideal with auto-controller watchband volume pump.The plating bath operating procedure adopts pneumatic blending, and temperature is at 50-55 ℃, and the pH value of plating bath maintains between the 7.0-9.5.The chemical nickel plating reaction is influenced by diffusion process.Chemical nickel-plating liquid stirred help improving the transmission speed of reactant to workpiece surface, also help simultaneously the disengaging of reaction product, not only can prevent plating leakage, pin hole, improve the coating visual appearance, and can prevent local superheating, this helps the stability of plating bath.In essence, stir the chemical ingredients and the pH value that have changed in workpiece/solution interface diffusion layer, therefore, the influence of stirring is important.When adopting steam or electric heater direct heating, solution must have pneumatic blending or continuous circulation system, and heated solution bamboo telegraph is opened.When bath pH value was low, the effect that pneumatic blending improves plating speed was more remarkable; Ultrasonic stirring helps improving plating speed when high pH value.Adopt pneumatic blending in the present invention.
Aftertreatment: toast and thermal treatment, be used to improve the adhesion performance of coating.
Further specify below by specific embodiment, but the present invention is not limited to following examples.
At first carry out cleaning by degreasing, alkali lye composition (containing sodium hydroxide 15-20g/L, yellow soda ash 15-30g/L, sodium phosphate 15-30g/L, Sodium dodecylbenzene sulfonate 2g/L), cleaning temperature 20-60 ℃, time 0.5-1 minute.
Weak acid is washed then, at room temperature cleans 0.5-2 minute with the hydrochloric acid soln of 100-200mL/L.
Electroplate in advance, pre-plating bath composition is identical with chemical nickel-plating liquid again, and its operational condition is: temperature 40-55 ℃, and voltage 2-4V, current density 0.2-0.4A/dm
2, time 1-2 minute.
Chemical nickel plating then.Technological specification is as follows:
Carry out aftertreatment at last: storing temperature 60-70 ℃, time 30-60min.
It is as follows that coating performance is detected in the plating back:
| Project | Test result |
| Thickness of coating | The 3-5 micron |
| The coating phosphorus content | 5%-8% |
| SaltSprayTest | Testing standard: salts solution 50 ± lg/L; PH value in the time of 35 ℃ should remain in the 6.5-7.2 scope; Rate of salt spray precipitation, 1.0-2.0ml/h (in the horizontal collecting region of 80cm2); Temperature in the proofing box in the efficiency test space is 35 ± 2 ℃; The test period internal spraying of regulation must not interrupt.After test specimen takes out in the salt air corrosion case, use the tap water flushing that is no more than 38 ℃, back to be dried is checked.Test after 24 hours, nothing is peeled off, and nothing is split, and is no wrinkling, no foaming phenomenon. |
| Adhesion performance | Be under 150 degrees centigrade the condition, to toast 10 minutes in temperature, no bubble, no wrinkling. |
Claims (10)
1. copper-alloy chemical nickeling process is characterized in that may further comprise the steps:
-cleaning by degreasing;
-weak acid is washed;
-pre-the plating;
-chemical nickel plating: carry out chemical nickel plating with the plating bath that contains following component, bath composition comprises that it is 7.0-9.5 that soluble nickel salt 20-30g/L, complexing agent 15-20g/L, hypophosphite reductive agent 20-30g/L, stablizer 2-5mg/L, pH regulator agent transfer to bath pH value, operational condition is: stir, bath temperature is controlled at 50-55 ℃;
-aftertreatment.
2. copper-alloy chemical nickeling process according to claim 1 is characterized in that: described pre-plating step operational condition is: temperature is 40-55 ℃, voltage 2-4V, current density 0.2-0.4A/dm
2, time 1-2 minute.
3. copper-alloy chemical nickeling process according to claim 1 is characterized in that: pre-plating bath composition is identical with chemical nickel-plating liquid in the described pre-plating step.
4. copper-alloy chemical nickeling process according to claim 1 is characterized in that: the complexing agent in the described chemical nickel-plating plating solution is a Trisodium Citrate.
5. copper-alloy chemical nickeling process according to claim 1 is characterized in that: the hypophosphite reductive agent in the described chemical nickel-plating plating solution is an inferior sodium phosphate.
6. copper-alloy chemical nickeling process according to claim 1 is characterized in that: the stablizer in the described chemical nickel-plating plating solution is a Potassium Iodate.
7. copper-alloy chemical nickeling process according to claim 1 is characterized in that: the pH regulator agent in the described chemical nickel-plating plating solution is ammoniacal liquor or alkali metal hydroxide.
8. copper-alloy chemical nickeling process according to claim 1 is characterized in that: pneumatic blending is adopted in the stirring in the operational condition of described electroless nickel step.
9. copper-alloy chemical nickeling process according to claim 1 is characterized in that: the described chemical nickel plating time is time 4-10 minute.
10. copper-alloy chemical nickeling process according to claim 1 is characterized in that: described post-processing operation technology is storing temperature 60-70 ℃, time 30-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100358224A CN100476026C (en) | 2005-07-11 | 2005-07-11 | Copper-alloy chemical nickeling process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100358224A CN100476026C (en) | 2005-07-11 | 2005-07-11 | Copper-alloy chemical nickeling process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1896307A CN1896307A (en) | 2007-01-17 |
| CN100476026C true CN100476026C (en) | 2009-04-08 |
Family
ID=37608947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100358224A Expired - Fee Related CN100476026C (en) | 2005-07-11 | 2005-07-11 | Copper-alloy chemical nickeling process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100476026C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI683927B (en) * | 2014-11-26 | 2020-02-01 | 德商德國艾托特克公司 | Plating bath and method for electroless deposition of nickel layers |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104372314A (en) * | 2013-08-12 | 2015-02-25 | 国家电网公司 | Condenser brass tube chemical nickel plating method |
| CN103484841B (en) * | 2013-10-10 | 2016-07-20 | 青岛黎马敦包装有限公司 | A kind of production technology of high accuracy and the fine gold stamping version of hardness |
| 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 |
| 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 |
-
2005
- 2005-07-11 CN CNB2005100358224A patent/CN100476026C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 化学镀技术. 伍学高，李铭华，黄渭成，306-307，四川科学技术出版社. 1985 |
| 化学镀技术. 伍学高，李铭华，黄渭成，306-307，四川科学技术出版社. 1985 * |
| 提高电连接器铝外壳化学镀镍质量的途径. 沈涪.电镀与涂饰，第22卷第3期. 2003 |
| 提高电连接器铝外壳化学镀镍质量的途径. 沈涪.电镀与涂饰，第22卷第3期. 2003 * |
| 碱性化学镀镍工艺研究. 张胜利，冯绍彬，肖峰，雷振斌.郑州轻工业学院学报，第8卷第1期. 1993 |
| 碱性化学镀镍工艺研究. 张胜利，冯绍彬，肖峰，雷振斌.郑州轻工业学院学报，第8卷第1期. 1993 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI683927B (en) * | 2014-11-26 | 2020-02-01 | 德商德國艾托特克公司 | Plating bath and method for electroless deposition of nickel layers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1896307A (en) | 2007-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100476026C (en) | Copper-alloy chemical nickeling process | |
| CN102051604B (en) | Austenitic stainless steel surface chemical nickel-phosphorus plating method | |
| CN100476029C (en) | Direct chemical nickeling process for pressed-cast aluminum alloy | |
| CN100476027C (en) | Chemical nickeling liquid and process thereof | |
| CN100476025C (en) | Aqueous alkaline zincate solutions and method for depositing zincate coating on aluminium or aluminium substrate | |
| CN102051605B (en) | Method for anti-corrosive surface treatment of aluminum or aluminum alloy product | |
| CN101225518A (en) | Hot-dip galvanizing with electroless ni pre-plating method for controlling thickness of silicon-containing active steel plating | |
| TW200902757A (en) | Electroless gold plating bath, electroless gold plating method and electronic parts | |
| CN110117783A (en) | A kind of method of Electroless Nickel Plating of Aluminum Alloy mixed metal activation | |
| CN1936079A (en) | Method for chemically-plating nickel-phosphor alloy cladding on magnesium alloy surface | |
| US3024134A (en) | Nickel chemical reduction plating bath and method of using same | |
| CN109355645A (en) | A kind of method of weakly acidic pH chemical plating high W content Ni-W-P alloy layer | |
| CN101275222B (en) | Nickel-phosphorus-polytetrafluorethylene composite plating solution | |
| CN103215574B (en) | Magnesium-alloy chemical nickel plating solution and nickel plating process thereof | |
| CN101709460A (en) | Chemical Ni-P plating anode composite plating layer structure and preparation process thereof | |
| CN105525320A (en) | Nickel plating method used for heating plate | |
| CN101831645B (en) | Cemented carbide steelwork surface electroless copper plating method | |
| CN100451170C (en) | Process for preparing pretreatment layer and coating on magnesium and magnesium alloy surface | |
| CN101177784A (en) | Magnesium alloy surface chemical plating process | |
| JP3035676B2 (en) | Method for electroless nickel plating on zinc-aluminum alloy, composition for catalytic treatment, composition for activation treatment, and composition for electroless nickel strike plating | |
| US20040031694A1 (en) | Commercial process for electroplating nickel-phosphorus coatings | |
| CN102877044A (en) | Method for producing environment-friendly lead-free electroless nickel immersion gold | |
| CN105803431B (en) | A kind of chemically coating nickel by magnesium-alloy liquid, preparation method and its nickel plating process | |
| CN110965053A (en) | Acidic chemical nickel plating method and solution | |
| JPS6353278B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090408 Termination date: 20110711 |