CN1546726A - Method for chemical plating nickel phosphor alloy - Google Patents
Method for chemical plating nickel phosphor alloy Download PDFInfo
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- CN1546726A CN1546726A CNA2003101072634A CN200310107263A CN1546726A CN 1546726 A CN1546726 A CN 1546726A CN A2003101072634 A CNA2003101072634 A CN A2003101072634A CN 200310107263 A CN200310107263 A CN 200310107263A CN 1546726 A CN1546726 A CN 1546726A
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Abstract
The invention discloses a method for chemical plating nickel phosphor alloy, wherein the chemical plating bath comprises the main constituents of the mixed solution of nickel hypophosphite and hypophosphorous acid, sodium citrate, ethyl acetate, sodium glucoheptonate and trace amount of lead, wherein the nickel hypophosphite and hypophosphorous acid mixed solution is prepared through electrolytic method. The invention realizes substantially improved coating property.
Description
Technical Field
The invention relates to the field of surface chemical treatment of materials, in particular to a novel method for chemically plating a nickel-phosphorus alloy.
Background
Chemical plating is a surface strengthening method for improving the surface wear resistance and corrosion resistance of materials such as metal and the like, and has the advantages of uniform plating layer, capability of being carried out on the surfaces of non-conductor and semiconductor materials, simple process, no need of a power supply, strong binding force and the like. Chemical nickel plating is to deposit a nickel layer on the surface of a substrate with catalytic activity immersed in a plating bath, so that the reaction is continued and a metal nickel-phosphorus alloy protective layer is gradually formed. Conventional electroless nickel plating baths are generally composed of a primary salt (metallic nickel salt, e.g. NiSO)4Or NiCl2) Reducing agents (sodium hypophosphite), complexing agents (various organic acids such as: citric acid, acetic acid, succinic acid, lactic acid, tartaric acid and the like and salts thereof), catalysts (organic salts), buffering agents (acetic acid, sodium acetate and the like), stabilizing agents (thiourea, heavy metal salts) and the like. The electroless nickel plating principle is complex, and most people accept the atomic hydrogen theory at present, and the reaction equation is as follows:
the nickel and the phosphorus are reduced simultaneously and are deposited on the substrate together to form the nickel-phosphorus alloy coating.
During the plating process of the traditional chemical nickel plating bath, a large amount of phosphite ions and Na are generated+And SO4 2-Or Cl-When these ions accumulate to a certain concentration, the plating solution ages, the plating rate is significantly reduced or even no plating rate is present, and the plating solution must be replaced. The aging liquid must be treated before being discharged into the environment, and if the aging liquid is not treated properly, the environment is inevitably burdened. Large amounts of useful components are also lost during the treatmentE.g. Ni2+、H2PO2 -And complexing agents, buffers, etc., which greatly increase the cost of electroless nickel plating and severely limit the forward development of the electroless nickel plating industry. With the continuous expansion of the application field of electroless nickel plating, especially the application in high-end fields such as aerospace, electronic industry and the like, the traditional electroless nickel plating technology can not meet the requirements of the fields. In recent years, with the continuous improvement of nickel hypophosphite preparation technology, foreign experts and scholars (Jeanneret, Gilbert, Brunner, U S Patent, 6030593; Richard, Andereile Joseph et al, U S Patent, 6200448) propose that nickel hypophosphite can be used to replace nickel sulfate and sodium hypophosphite to carry out chemical nickel plating, the nickel hypophosphite can be used as both an oxidizing agent and a reducing agent, and during plating, an auto-redox reaction occurs. The method has the main advantage of eliminating impurity ions such as Na+And SO4 2-Or Cl-The interference of plasma can obtain a nickel-phosphorus alloy coating with higher quality; and the treatment of the aging liquid is easy, and the discharge of waste is reduced. Horikawa, a japanese scholars; ken (Horikawa; Ken, Mita; Muneo, Nakao; Hidehiro, U.S. Pat. No. 6245389) successfully applied electroless nickel plating using a metathesis reaction of nickel chloride or sulfate with sodium hypophosphite to produce nickel hypophosphite. But do notThe nickel hypophosphite prepared by the double decomposition method has lower purity, and the main material Ni (H)2PO2)2·6H2The percentage of O is about 90-95%, because the product still contains 5-10% of Na2SO4Or NaCl, and the like, and therefore, the use of this material for electroless nickel plating has a disadvantage in that Na cannot be completely eliminated+And SO4 2-Or Cl-The interference of plasma impurity ions on chemical nickel plating influences the quality of a plating layer; the sodium hypophosphite for chemical nickel plating bath is used for regulating the concentration ratio of nickel ions to hypophosphite ions, and in the plating process, nickel hypophosphite and sodium hypophosphite are added to supplement consumed Ni2+And H2PO2 -Will certainly make Na+And SO4 2-Or Cl-Enrichment affects the life of the electroless nickel bath.
The mixed solution of nickel hypophosphite and hypophosphorous acid prepared by an electrolytic method (see the same-day patent application of the applicant: the method for preparing nickel hypophosphite by the electrolytic method) andthe hypophosphorous acid prepared by the electrolytic method (Chinese patent CN 1341779A) are successfully prepared, and the purity of the nickel hypophosphite product reaches more than 99 percent.
Disclosure of Invention
The invention aims to provide a method for chemically plating a nickel-phosphorus alloy, which can overcome the defects of the prior art. The invention adopts the mixed solution of the nickel hypophosphite and the hypophosphorous acid prepared by the electrolytic method to carry out chemical nickel plating, and the concentrated solution of the nickel hypophosphite and the hypophosphorous acid obtained by decompression and enrichment is used as a supplement liquid, thereby completely overcoming the defect of carrying out the chemical nickel plating by using the nickel hypophosphite prepared by a double decomposition method as a raw material and obtaining a high-quality plating layer. The invention greatly improves the plating speed and the service life of the plating bath, and can obtain a uniform, compact and bright nickel-phosphorus alloy plating layer.
The invention relates to a novel chemical nickel plating method which takes mixed solution of nickel hypophosphite and hypophosphorous acid as main raw materials, wherein the nickel hypophosphite is used as an oxidizing agent and a reducing agent, sodium citrate is used as a complexing agent, acetic acid is used as a buffering agent, sodium gluconate is used as a catalyst, and trace lead is used as a stabilizing agent. The mixed solution of nickel hypophosphite and hypophosphorous acid is prepared by an electrolytic method in the laboratory.
The method comprises the following specific steps:
the plated part is pretreated before plating to remove oil stain and oxide on the surface. The pretreatment process mainly comprises the following steps: chemical degreasing → water washing → mechanical polishing → water washing → acid washing activation → water washing → chemical plating of nickel phosphorus alloy.
Chemical oil removal: wherein the chemical degreasing composition is as follows:
Na2CO3(32g/L)
NaOH (20g/L)
Na3PO4(25g/L)
nonionic surfactant (7.5g/L)
The pretreatment is to ensure that the oil stains on the surface of the plating piece matrix are thoroughly removed, so that the surface is clean and rustless, and no oxide metal surface exists. And (3) chemically removing oil for 20-30 minutes at the temperature of 80 ℃.
Mechanical polishing: after the oil stain is treated, the workpiece must be polished in principle, and for the workpiece which cannot be polished, the pickling time is doubled when the last pickling and activating process is carried out. Degreasing solutions and pickling solutions must be replaced periodically.
Acid washing: (1: 1 hydrochloric acid), time: 5-10 minutes.
Washing with water: the water wash sequence avoids the common rinse, i.e., the rinse back into the previously used tank. If the pretreatment is improper, the deposition speed cannot be normally increased due to oil stains or impurity oxide scales during plating, so that the problems of high porosity, uneven thickness, unqualified bonding strength, tarnished appearance and the like of the plating layer are caused.
Acid washing and activating: 1: 9 sulfuric acid, time: 0.5-1 min.
Chemical plating of nickel-phosphorus alloy:
concentration of nickel ions: 4-8 g/L.
The pH value of the plating solution is 5-6, and the pH value of the plating bath is adjusted by ammonia water, preferably 5.5.
The molar ratio of the hypophosphite ions to the nickel ions is kept between 3 and 4. The invention prepares the mixed solution of nickel hypophosphite and hypophosphorous acid by an electrolytic method, wherein Ni is contained in the mixed solution2+Concentration of 4-8 g/L (0.07-0.14 mol/L), H2PO2 -The concentration is 13-35 g/L (0.20-0.54 mol/I).
The complexing agent is glycolic acid, lactic acid, propionic acid, succinic acid, malic acid, citric acid or corresponding salt thereof, and sodium citrate (Na) with the concentration of 20-45 g/L is selected3C6H5O·2H2O) as a complexing agent.
Catalyst and stabilizer: 15-20 g/L of sodium gluconate,
a buffering agent; 10 to 14ml/L of acetic acid,
temperature: 85-95 ℃, preferably 87-90 ℃.
2-3 ppm of trace lead (lead acetate).
Average plating speed: 12 um/h.
During the plating process, Ni2+When 10% is consumed, nickel hypophosphite and hypophosphorous acid solution are supplemented to supplement the consumed Ni2+And H2PO2 -To maintain Ni2+And H2PO2 -The proportion range ensures that the chemical plating process is continuously carried out; ammonia water is used as a pH regulator to stabilize the pH of the plating solution to about 5.5. The plating speed V (um/h) is measured with an accuracy of 1X 10-3The thickness difference of the sample before and after plating is measured by a micrometer of mm, and then the thickness difference is divided by the plating time.
The invention completely overcomes the defect of chemical nickel plating by using the nickel hypophosphite prepared by a double decomposition method as a raw material, and can obtain a high-quality plating layer. The chemical nickel plating bath can plate continuously for more than 6 periods, the average plating speed can reach 12um/h, and a uniform, compact and bright nickel-phosphorus alloy plating layer with metallic luster can be obtained.
The invention has the advantages that the plating layer is not influenced by impurity ions such as sodium ions, sulfate ions or chloride ions, the performance of the plating layer is greatly improved, the aging liquid can be recycled after being treated by simply removing phosphite ions, the environment is not polluted, and the invention belongs to clean production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a chemical nickel-phosphorus alloy plating layer with the thickness of 25 um.
FIG. 2 is an X-ray diffraction pattern of a chemical nickel-phosphorus alloy plating layer with the thickness of 30 um.
Detailed Description
Example 1
Firstly, preparing a mixed solution of nickel hypophosphite and hypophosphorous acid by an electrolysis method. See the application of 'method for preparing nickel hypophosphite by electrolytic process' on the same day.
Electrolytic miningUsing a six-chamber electrodialysis tank, wherein the anode material is a nickel plate, and the electrode area is 40cm2And the cathode is a stainless steel electrode. The anion-cation exchange membrane is purchased from Shanghai chemical plant, and the membrane area used in electrolysis is 70cm2. The volume of solution per compartment of the six-compartment electrodialysis cell was 450 mL. The initial solution in the anode chamber before electrolysis is 10g/L sulfuric acid, the raw material chamber is 400g/L sodium hypophosphite, the cathode chamber and the adjacent buffer chamber are both 10g/L sodium hydroxide, and the product chamber and the adjacent buffer chamber are both 10g/L nickel hypophosphite.
The working voltage is 10-15V
TABLE 1 shows Ni in the product compartment after 6 hours of electrolysis under different current conditions2+、H+And H2PO2 -The concentration of (c).
TABLE 1 product concentration at different operating currents
Ni2+Concentration H+Concentration H2PO2 -Concentration of
Current (A)
(g/L) (mol/L) (g/L) (mol/L) (g/L) (mol/L)
0.5 3.17 0.054 0.072 0.072 11.70 0.18
1.0 4.81 0.082 0.160 0.160 21.45 0.33
1.5 9.39 0.16 0.180 0.180 32.50 0.50
2.0 14.09 0.24 0.200 0.200 43.55 0.67
2.5 17.61 0.30 0.220 0.220 53.30 0.82
Controlling the electrolysis current to be 1.0-2.5A, and electrolyzing for 6 hours to obtain a mixed solution of nickel hypophosphite and hypophosphorous acid which can be directly used as a chemical nickel plating solution; the mixed solution was enriched underreduced pressure to obtain a concentrated solution as a supplement.
Example 2
The mixed solution of the nickel hypophosphite and the hypophosphorous acid is used for preparing 1 liter of plating solution, and the plating solution comprises the following components: nickel ion (Ni)2+)6g/L, hypophosphite ion (H)2PO2 -)21g/L, 45g/L of sodium citrate, 20g/L of sodium gluconate, 14ml/L of acetic acid and trace lead (2-3 ppm) (lead acetate). The concentrations of nickel ions and hypophosphite ions in the supplementing liquid are respectively as follows: 36g/L and 126 g/L. Putting the plating solution into a 2L glass plating tank, controlling the temperature of the plating bath to 87-90 ℃ by using a constant-temperature water bath box, and adjusting the pH value of the plating bath to 5.5 by using ammonia water. Four pieces of the treated steel plates (50 mm. times.30 mm. times.1.20 mm) were immersed in a plating bath, and after 1 hour, the plated pieces were taken out and washed with distilled water, and the thicknesses of the plated layers were measured as 16um, 17um, 18um, and 18um, respectively. The surface of the plated part can be seen by naked eyes to have a layer of uniform, compact and bright plating layer.
The steel plate treatment process comprises the following steps: at a temperature of 80 ℃, mixing the following components in a mixed solution:
Na2CO3(32g/L)
NaOH (20g/L)
Na3PO4(25g/L)
nonionic surfactant (7.5g/L)
Treating for 25 min, washing with water, mechanically polishing, washing with 1: 1 hydrochloric acid for 5 min, washing with water, activating with 1: 9 sulfuric acid for 0.5 min, and washing with water.
Example 3
A new bath was prepared without sodium gluconate and the other experimental conditions were the same as in example 2. After half an hour of plating, it was found that the plating bath started to undergo redox reaction, a small area of plating layer was formed at the bottom of the glass beaker, and the stability of the plating bath was lowered. After one hour, the plated article was taken out and washed with distilled water, and the thicknesses of the plating layers were measured to be 9um, 7um, 8um, and 6um, respectively. The tarnish, the poor uniformity and the poor compactness of the plating surface are observed by naked eyes, and obvious pinholes appear.
Example 4
The experimental conditions were the same as in example 2, and the electroless nickel plating bath was continuously applied. In the process of plating, the plating solution is added,each time Ni2+When 10% of the solution is consumed (approximately every 40 minutes), the corresponding nickel hypophosphite and hypophosphorous acid solution are replenished; ammonia water was added periodically to stabilize the bath pH at 5.5. After continuous plating for 6 periods, the plating speed averagely reaches 12um/h, and no precipitation is generated in the plating bath. The plating layers of all the plated parts are uniform, compact and bright. The coating was tested using a plasma emission spectrometer ICP-9000(N + M) manufactured by the american company t.j.a, with a phosphorus content of about 13%, which is a high-phosphorus coating; the crystal form of the coating is analyzed by a Japanese physical D/MAX-2500 type X-ray diffractometer, and an XRD spectrogram (figures 1 and 2) shows a broadened dispersion peak near 45 ℃ at 2 theta, and the peak is a characteristic peak of the Ni-P amorphous alloy, which indicates that the coating is in an amorphous structure.
Example 5
Three plated articles (50 mm. times.30 mm. times.1.20 mm) obtained in example 4 were picked and subjected to corrosion test. The weighing was carried out using an AB104-N electronic balance. The specific situation is shown in table 2:
TABLE 2 Corrosion of the coating
Etching solution 10% NaOH solution 10% H2SO4Solution 5% NaCl solution
Coating thickness (um) 171618
Weight before Corrosion (g) 14.517314.619114.5314
Post-etch weight (g) 14.516414.397714.5152
Corrosion time (h) 168168168
Corroded weight (mg) 0.9221.422.0
Corrosion rate (mg/cm)2·h) 1.78×10-44.39×10-24.37×10-3
As can be seen, the chemical nickel-phosphorus alloy plating layer has strong corrosion resistance in alkaline solution and is inorganicSalt such as NaCl solution. The weakest corrosion resistance is in the oxidizing acids, such as H2SO4、HNO3And the like.
Example 6
According to the national standard GB 6461-86 of the people's republic of China, namely the rating of an electroplating sample after a corrosion test of a metal covering layer on a covering layer with a substrate as a cathode, a group of samples (plated parts) are selected and exposed for 60 days in the outdoor atmosphere, and the average protection grade of the group of samples is obtained by contrasting an appendix B circular point diagram of the standard, wherein the appendix B circular point diagram is 8.
TABLE 3 coating protection rating
| Sample number | 1234567 averaging |
| Protection class | 9 8 7 7 8 9 7 8 |
In order to verify the adhesion of the plating layer, the plated article was bent at an angle and the change of the plating layer at the bent portion of the plated article was examined. In all experimental plated articles, there was no plating peeling, indicating that the adhesion of the plating was high.
Claims (8)
1. A method for chemically plating nickel-phosphorus alloy is characterized in that a mixed solution of nickel hypophosphite and hypophosphorous acid is used as a main raw material, and the nickel hypophosphite is used as an oxidant and a reducing agent; hypophosphorous acid is used for adjusting the concentration ratio of nickel ions to hypophosphite ions; sodium citrate as a complexing agent; acetic acid as a buffer; sodium gluconate as catalyst and stabilizer; trace amounts of lead as a stabilizer; the method comprises the following specific steps:
the plating piece is pretreated before plating to remove oil stains and oxides on the surface, and the pretreatment process mainly comprises the following steps: chemical degreasing → water washing → mechanical polishing → water washing → acid washing activation → water washing → chemical nickel phosphorus alloy plating;
chemical oil removal: whereinthe chemical degreasing composition is as follows:
Na2CO332g/L
NaOH 20g/L
Na3PO425g/L
nonionic surfactant 7.5g/L
Carrying out chemical degreasing for 20-30 minutes at the temperature of 80 ℃;
acid washing: 1: 1 hydrochloric acid, time: 5-10 minutes. Acid washing and activating: 1: 9 sulfuric acid, time: 0.5-1 minute;
concentration of nickel ions in plating solution: 4-8 g/L;
the pH value of the plating solution is 5-6;
the molar ratio of hypophosphite ions to nickel ions is 3-4;
the complexing agent is 20-45 g/L glycolic acid, lactic acid, propionic acid, succinic acid, malic acid, citric acid or corresponding salts thereof;
catalyst and stabilizer: 15-20 g/L of sodium gluconate,
a buffering agent; 10 to 14ml/L of acetic acid,
temperature: 85-95 ℃;
trace lead: 2 to 3 ppm.
Average plating speed: 12 um/h.
2. The method of electroless plating nickel-phosphorus alloy according to claim 1, wherein said mixed solution of nickel hypophosphite and hypophosphorous acid contains Ni2+Concentration of 4-8 g/L (0.07-0.14 mol/L), H2PO2 -The concentration is 13-35 g/L (0.20-0.54 mol/L); said nickel hypophosphite and hypophosphorous acidThe mixed solution is prepared by an electrolytic method.
3. A method of electrolessly plating a nickel-phosphorus alloy as recited in claim 1, wherein said plating bath temperature is controlled to be 87 ℃ to 90 ℃.
4. The method of electroless plating nickel-phosphorus alloy according to claim 1, wherein the complexing agent is sodium citrate.
5. The method of electroless nickel-phosphorus alloy plating according to claim 1, wherein said pH value is stabilized at 5.5.
6. The method of electroless nickel-phosphorus alloy plating according to claim 1, wherein said lead is lead acetate.
7. A method of electrolessly plating a nickel-phosphorus alloy as recited in claim 1, wherein Ni is present in said plating bath2+When 10% is consumed, nickel hypophosphite and hypophosphorous acid solution are supplemented to supplement the consumed Ni2+And H2PO2 -。
8. A method for electroless plating of nickel-phosphorus alloys according to claim 7, wherein said additional mixed solution of nickel hypophosphite and hypophosphorous acid is a concentrated solution obtained by electrolysis and concentration under reduced pressure.
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| CN101942651A (en) * | 2010-09-28 | 2011-01-12 | 蔡乐勤 | Zero-discharge chemical nickel-plating technology |
| CN101634019B (en) * | 2008-07-21 | 2011-10-26 | 中国科学院宁波材料技术与工程研究所 | Pretreatment method for chemical nickel plating of zinc/aluminum-based alloy and application thereof |
| CN101413912B (en) * | 2008-11-06 | 2012-07-25 | 浙江工业大学 | Method for measuring phosphate radical concentration in chemical nickel plating solution |
| CN103103505A (en) * | 2011-11-14 | 2013-05-15 | 绿阳光电股份有限公司 | Chemical bath deposition system |
| CN104131272A (en) * | 2014-07-28 | 2014-11-05 | 湖南工程学院 | Zero emission type chemical nickel plating liquid |
| CN104746055A (en) * | 2015-04-27 | 2015-07-01 | 南京宁美表面技术有限公司 | High-stability chemical nickel plating solution and chemical plating method |
| CN105695962A (en) * | 2016-03-10 | 2016-06-22 | 中南大学 | Solution for chemically plating nickel on surface of non-catalytic active material and plating process for solution |
| CN109136891A (en) * | 2017-06-18 | 2019-01-04 | 罗奕兵 | A kind of nickel-phosphor amorphous alloy composite fibre and preparation method |
| CN109244403A (en) * | 2018-09-12 | 2019-01-18 | 烟台厚旭能源科技有限责任公司 | A kind of method that iteration calendering prepares lead carbon composite |
| CN109286004A (en) * | 2018-09-12 | 2019-01-29 | 烟台厚旭能源科技有限责任公司 | A kind of preparation method of lead carbon composite |
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| RU2226228C2 (en) * | 1999-08-20 | 2004-03-27 | Дю Пон Де Немур Энтернасьональ С.А. | METHOD OF ELECTROCHEMICAL PRODUCTION OF Ni(0) PHOSPHITE AND DIPHOSPHITE COMPLEXES |
| CN1132965C (en) * | 2001-09-07 | 2003-12-31 | 南开大学 | Method for preparing phosphorous acid by using electrolytic method |
| CN1172028C (en) * | 2001-09-07 | 2004-10-20 | 南开大学 | Method for preparing hypophosphorous acid by using electrolytic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101634019B (en) * | 2008-07-21 | 2011-10-26 | 中国科学院宁波材料技术与工程研究所 | Pretreatment method for chemical nickel plating of zinc/aluminum-based alloy and application thereof |
| CN101413912B (en) * | 2008-11-06 | 2012-07-25 | 浙江工业大学 | Method for measuring phosphate radical concentration in chemical nickel plating solution |
| CN101942651B (en) * | 2010-09-28 | 2012-07-25 | 蔡乐勤 | Zero-discharge chemical nickel-plating technology |
| CN101942651A (en) * | 2010-09-28 | 2011-01-12 | 蔡乐勤 | Zero-discharge chemical nickel-plating technology |
| CN103103505A (en) * | 2011-11-14 | 2013-05-15 | 绿阳光电股份有限公司 | Chemical bath deposition system |
| CN104131272B (en) * | 2014-07-28 | 2017-04-05 | 湖南工程学院 | A kind of zero-emission type chemical nickel-plating liquid |
| CN104131272A (en) * | 2014-07-28 | 2014-11-05 | 湖南工程学院 | Zero emission type chemical nickel plating liquid |
| CN104746055A (en) * | 2015-04-27 | 2015-07-01 | 南京宁美表面技术有限公司 | High-stability chemical nickel plating solution and chemical plating method |
| CN105695962A (en) * | 2016-03-10 | 2016-06-22 | 中南大学 | Solution for chemically plating nickel on surface of non-catalytic active material and plating process for solution |
| CN105695962B (en) * | 2016-03-10 | 2017-12-29 | 中南大学 | A kind of solution and its plating technology of the chemical nickel plating on non-catalytic material surface |
| CN109136891A (en) * | 2017-06-18 | 2019-01-04 | 罗奕兵 | A kind of nickel-phosphor amorphous alloy composite fibre and preparation method |
| CN109244403A (en) * | 2018-09-12 | 2019-01-18 | 烟台厚旭能源科技有限责任公司 | A kind of method that iteration calendering prepares lead carbon composite |
| CN109286004A (en) * | 2018-09-12 | 2019-01-29 | 烟台厚旭能源科技有限责任公司 | A kind of preparation method of lead carbon composite |
| CN109286004B (en) * | 2018-09-12 | 2022-03-01 | 东方旭能(山东)科技发展有限公司 | Preparation method of lead-carbon composite material |
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