CN101289740B - Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy - Google Patents
Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy Download PDFInfo
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- CN101289740B CN101289740B CN2008100647196A CN200810064719A CN101289740B CN 101289740 B CN101289740 B CN 101289740B CN 2008100647196 A CN2008100647196 A CN 2008100647196A CN 200810064719 A CN200810064719 A CN 200810064719A CN 101289740 B CN101289740 B CN 101289740B
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Abstract
The invention provides a chemical nickel tungsten phosphorus plating solution for magnesium alloy, which consists of 10-20 g/L of nickel sulfate, 7-15 g/L of sodium tungstate, 29-50 g/L of sodium citrate, 14-30 g/L of sodium hypophosphite, 14-30 g/L of sodium carbonate, 5-12 g/L of ammonium bifluoride, additive accounting for 0.00005-0.003 percent of total weight and the balance being water. The solution uses the nickel sulfate instead of basic nickel carbonate for introduction and has the sodium tungstate added in, so as to ensure that a plating layer is better in corrosion resistance and wear resistance, and the plating solution is convenient to prepare and much lower in cost. The solution solves the problem that the chemical nickel plating layer is low in corrosion resistance and wear resistance.
Description
(1) technical field
What the present invention relates to is a kind of chemical plating bath prescription, specifically is a kind of magnesium alloy multiple elements chemical plating electroplate liquid formulation.
(2) background technology
Magnesium alloy is structural metal the lightest in the industrial application, because its proportion is little, and the intensity height, good heat conductivity has good damping shock absorption and electro-magnetic screen function again, therefore has to substitute the engineering plastics that are difficult to reclaim, as the shell structure part, be applied to mobile phone, in the electronic products such as notebook computer, it is light to satisfy electronic product, thin, short, little and good heat dissipation improves the working efficiency of machine and the requirement in work-ing life.The former magnesium output of China accounts for the No. 1 in the world at present.
In order to prevent the magnesium alloy corrosion, general at present employing chemically coated nickel method protects magnesium alloy.For example, CN 1598053A discloses a kind of nickel chemical plating technology that carries out on magnesium alloy, and this technology is invaded magnesium alloy in the plating bath of chemical nickel plating, bathes 0.5-4 hour at 70-98 ℃.The electrode potential of mentioning nickel among the CN1598053A is-0.25V.
Traditional magnesium alloy chemical depositing process long flow path, operational difficulty, process is difficult to control, and cost is higher.Traditional plating Ni-P coating porosity is bigger, and corrosion resistance nature is not good enough, and nickel dam is limited to the protection of magnesium alloy substrate.
Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy is filled a prescription as a result according to the retrieval, main employing basic nickel carbonate or sodium-acetate are main salt, in the recent research many with single nickel salt as main salt, utilization hydrogen fluoride is as inhibiter, it prepares inconvenient, requirement pretreatment technology height, strict, and environmental pollution is comparatively serious.The present invention adopts in the research single nickel salt as main salt, adopts ammonium bifluoride as inhibiter, utilizes optimality analysis, adjusts each main part concentration proportioning, and prescription adopts low tungsten, seeks the optimization proportioning.Its preparation is simple, pollutes lessly, and required pre-treatment is with general phosphoric acid-ammonium hydrogen fluoride solution processing, and the pre-treatment requirement is comparatively simple.Help industrial production, utilizations such as test.
(3) summary of the invention
The object of the present invention is to provide a kind of coating erosion resistance, wear resisting property of making better, and the plating bath preparation is convenient, the nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy that cost is low.
The object of the present invention is achieved like this:
It accounts for the additive of gross weight 0.00005-0.003% by single nickel salt 10-20g/L, sodium wolframate 7-15g/L, Trisodium Citrate 29-50g/L, inferior sodium phosphate 14-30g/L, yellow soda ash 14-30g/L, ammonium bifluoride 5-12g/L, additive and the water of surplus is formed, and described additive is a kind of in the acetate of thiocarbamide, plumbous acetate, cadmium or the Potassium Iodate.
Plating bath preparation method provided by the invention is identical with conventional plating bath preparation method.The preparation of chemical plating solution: dissolve above-mentioned medicine respectively with a small amount of distilled water or deionized water earlier, mix and be diluted to requiring concentration then, adjust the pH value of solution value, so just finished the layoutprocedure of plating bath to 6.0-10.0.
Use the invention provides plating bath magnesium alloy workpiece plating stirring means is adopted ultrasonic oscillation.Plating temperature is 60-90 ℃.
Before the magnesium alloy workpiece plating, should carry out pre-treatment to magnesium alloy work-piece surface, pre-treatment comprises degreasing, alkali cleaning and a step reactivation process.Clean up with distilled water between each step, and make its residence time in air short as far as possible.After having plated, the reply magnesium alloy workpiece is washed and is dry.Wherein, degreasing in the pre-treatment, the washing of alkali cleaning and aftertreatment, the exsiccant step is thought conventionally known to one of skill in the art, does not repeat them here.
The present invention is directed to matrix corrosion and the measure of pH value variation issue that magnesium alloy produces in plating bath has: before the plating magnesium alloy is carried out activation treatment one time in phosphoric acid-hydrogen fluorine ammonium activation solution, magnesium alloy workpiece forms one deck fluorochemical protective membrane, it is the energy stable existence in plating bath, can shield to matrix; Add quantitative fluorochemical in plating bath, certain density fluorion can be repaired damaged fluorinated film, the protection matrix; The pH value changes to adopt adds yellow soda ash as buffer reagent.
Electroless plating in pressing the plating bath of formulated of the present invention, the matrix magnesium alloy can not be subjected to bath corrosion, and the coating that obtains is smooth, and coating has corrosion resistance preferably in conjunction with good.Adopt the present invention to obtain coating and can be used as the independent protective layer of magnesium alloy, also can be used as galvanized bottom.
The present invention replaces basic nickel carbonate to introduce with single nickel salt, and adds sodium wolframate, makes the coating erosion resistance, and wear resisting property is better, and the plating bath preparation is convenient, and cost greatly reduces.Solve the chemical Ni-plating layer corrosion resistance nature, the problem that wear resisting property is lower.
In plating bath, comparatively expensive basic nickel carbonate or the sodium-acetate of price, the complicacy when price has greatly reduced and reduced preparation have been replaced with Trisodium Citrate; Adding sodium wolframate is that secondary salt is beneficial to the obstruction hole in order to deposit simultaneously at matrix surface and nickel, the hardness of raising coating; Use yellow soda ash as buffer reagent, help controlling plating bath Ph value and change, help the uniform deposition of electroless plating.As magnesium alloy chemical plating plating bath, adopt ammonium bifluoride among the present invention, replaced ammonium bifluoride and hydrogen fluoride mixing solutions in the former plating bath, help the protection of environment, the dangerous reduction.By the pollution that has reduced process complexity and environment in the novel process in above analysis and the traditional technology, and preparation is convenient, and the coating porosity helps the raising of its erosion resistance raising and hardness more for a short time.
(4) description of drawings
Fig. 1 is the anodic polarization curves of AZ91D sample and Electroless Plating Ni-W-sample; Wherein corrosive fluid is a 3.5%NaCl solution, and sweep velocity is 1mV/S.
Fig. 2 is the alternating-current impedance figure of AZ91D sample and Electroless Plating Ni-W-P sample; Wherein corrosive fluid is a 3.5%NaCl solution.
Fig. 3 is the alternating-current impedance figure of AZ91D sample; Wherein corrosive fluid is a 3.5%NaCl solution.
(5) embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1: take by weighing medicine in following ratio: single nickel salt 11.5g, sodium wolframate 7.6g, Trisodium Citrate 30.3g, inferior sodium phosphate 15.2g, yellow soda ash 15.2g, ammonium bifluoride 6.0g, Potassium Iodate 0.0001g, earlier above-mentioned medicine is used a small amount of dissolved in distilled water respectively, mixed diluting is to 1L then, and regulating bath pH value with ammoniacal liquor is 9.0.
With area is 7cm
2Magnesium alloy AZ91D go out fat through acetone, alkalescence is fuel-displaced, a step activation treatment is put into the chemical plating fluid that is heated to 85 ± 2 ℃, ultrasonic oscillation plating 2 hours.
After tested, binding force of cladding material is qualified, and overlay coating microhardness (Hv) is 465.
Can find out significantly that from Fig. 1 the AZ91D sample is an active dissolution, and Electroless Plating Ni-W-P sample, not only corrosion potential has improved greatly, and very long passivation region has been arranged, and corrosion current is far smaller than the AZ91D sample.Corrosion potential is high more, shows that erosion resistance is good more.So the erosion resistance of Electroless Plating Ni-W-P sample has improved greatly.
The impedance arc that also can obviously find out Electroless Plating Ni-W-P sample from Fig. 2 is far longer than the AZ91D sample, and the impedance arc is big more, and erosion resistance is just big more.So the erosion resistance of Electroless Plating Ni-W-P sample improves greatly.
Embodiment 2: press single nickel salt 18, sodium wolframate 13g, Trisodium Citrate 40g, inferior sodium phosphate 18g, yellow soda ash 18g, ammonium bifluoride 10g, thiocarbamide 0.0001g in addition
With area is 7cm
2Magnesium alloy AZ91D go out fat through acetone, alkalescence is fuel-displaced, a step activation treatment is put into the chemical plating fluid that is heated to 85 ± 2 ℃, ultrasonic oscillation plating 2 hours.The successful electroless plating of matrix energy, and every index is better than embodiment 1 coating performance.
Claims (1)
1. nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy, it is characterized in that: it accounts for the additive of gross weight 0.00005-0.003% by single nickel salt 10-20g/L, sodium wolframate 7-15g/L, Trisodium Citrate 29-50g/L, inferior sodium phosphate 14-30g/L, yellow soda ash 14-30g/L, ammonium bifluoride 5-12g/L, additive and the water of surplus is formed, and described additive is a kind of in the acetate of thiocarbamide, plumbous acetate, cadmium or the Potassium Iodate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2008100647196A CN101289740B (en) | 2008-06-13 | 2008-06-13 | Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy |
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| CN2008100647196A CN101289740B (en) | 2008-06-13 | 2008-06-13 | Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy |
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| CN101289740A CN101289740A (en) | 2008-10-22 |
| CN101289740B true CN101289740B (en) | 2010-07-07 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560449A (en) * | 2011-10-31 | 2012-07-11 | 森鹤乐器股份有限公司 | Plating solution for electroless-plating nickel, tungsten and phosphorus alloy of zinc alloy die castings and preparation method thereof |
| CN102517572A (en) * | 2011-12-06 | 2012-06-27 | 长安大学 | Chemical plating nickel-tungsten-phosphorus alloy solution for magnesium alloy and treatment process thereof |
| CN102747344A (en) * | 2011-12-08 | 2012-10-24 | 广西师范大学 | Chemical nickel plating solution and preparation method thereof, method for carrying out nickel plating on nano-LiFePO4/C composite material by using chemical nickel plating solution, and resulting product thereof |
| CN102634781A (en) * | 2012-05-11 | 2012-08-15 | 森鹤乐器股份有限公司 | Plating solution for chemically plating nickel tungsten phosphorus alloy for zinc alloy die-casting piece and preparation method of plating solution |
| CN103484839B (en) * | 2013-10-10 | 2016-03-02 | 江门市九星科技材料有限公司 | A kind of metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating and method |
| CN108796478B (en) * | 2018-06-29 | 2020-07-07 | 林忠华 | Electroless nickel-tin-tungsten-phosphorus amorphous multifunctional alloy plating solution and plating layer thereof |
| CN114059053B (en) * | 2021-11-09 | 2023-10-10 | 苏州汉宜纳米新材料有限公司 | Electroless Ni-W-P plating solution and preparation method thereof, ni-W-P plating layer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598052A (en) * | 2004-08-02 | 2005-03-23 | 吉林大学 | Magnesium alloy chemical plating nickle solution and its plating method |
| CN1598053A (en) * | 2004-08-05 | 2005-03-23 | 湖南大学 | Plating solution of magnesium alloy nickle sulfate main salt and technology of chemical plating thereof |
| US6887320B2 (en) * | 2002-02-11 | 2005-05-03 | United Technologies Corporation | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| CN101173351A (en) * | 2006-10-31 | 2008-05-07 | 佛山市顺德区汉达精密电子科技有限公司 | Chemical nickel plating solution for magnesium alloy and nickeling technique thereof |
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- 2008-06-13 CN CN2008100647196A patent/CN101289740B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6887320B2 (en) * | 2002-02-11 | 2005-05-03 | United Technologies Corporation | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| CN1598052A (en) * | 2004-08-02 | 2005-03-23 | 吉林大学 | Magnesium alloy chemical plating nickle solution and its plating method |
| CN1598053A (en) * | 2004-08-05 | 2005-03-23 | 湖南大学 | Plating solution of magnesium alloy nickle sulfate main salt and technology of chemical plating thereof |
| CN101173351A (en) * | 2006-10-31 | 2008-05-07 | 佛山市顺德区汉达精密电子科技有限公司 | Chemical nickel plating solution for magnesium alloy and nickeling technique thereof |
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Assignee: Hua Feng marine heavy anti-corrosion New Material Co. Ltd. Assignor: Harbin Engineering Univ. Contract record no.: 2012320000277 Denomination of invention: Nickel-tungsten-phosphorus bath for chemical plating of magnesium alloy Granted publication date: 20100707 License type: Exclusive License Open date: 20081022 Record date: 20120322 |
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