CN103726036A - Environment-friendly high-brightness medium-phosphorus chemical nickel-plating additive - Google Patents
Environment-friendly high-brightness medium-phosphorus chemical nickel-plating additive Download PDFInfo
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- CN103726036A CN103726036A CN201410031854.6A CN201410031854A CN103726036A CN 103726036 A CN103726036 A CN 103726036A CN 201410031854 A CN201410031854 A CN 201410031854A CN 103726036 A CN103726036 A CN 103726036A
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Abstract
The invention discloses an environment-friendly high-brightness medium-phosphorus chemical nickel-plating additive which is composed of components A and B, wherein the component A comprises the following raw materials: a 2-5mg/L mixture of nano copper and a soluble copper salt, 2-4mg/L rhenium sulfate, 1-4mg/L sodium allysulfonate (ALS), a complexing agent, a stabilizer, and 20-40g/L NaOH; the component B comprises the following raw materials: 1-4mg/L 1,4-bis(2-hydroxyethoxy)-2-butyne (BEO), 1-3mg/L N,N-diethylaminopropyne (DEP), 1-4mg/L dibenzenesulfonimide (BBI), and 2-4mg/L sodium hydroxymethanesulphonate (PN). The formula of the environment-friendly high-brightness medium-phosphorus chemical nickel-plating additive provided by the invention contains no heavy metal ions such as cadmium and lead, and is harmless to the environment; if applied to a chemical nickel-plating solution, the additive is capable of keeping the plating solution stable so that the obtained coating is even and compact, low in porosity, high in brightness and good in nitric acid resistance; more specifically, even though the nickel coating is soaked in concentrated nitric acid for 300 seconds, the nickel coating does not change color.
Description
Technical field
The present invention relates to phosphorus chemistry nickel plating additive and preparation method thereof in the high light of a kind of environment-friendly type.
Background technology
Chemical nickel plating can be described as again electroless nickel plating, is relying on the chemical reaction of autocatalysis in the process for treating surface of metallic surface nickel deposited, nickel alloy plating layer containing in the solution of nickel salt, reductive agent and other ancillary component.The coating that above technique obtains has the advantages such as hardness is higher, solidity to corrosion good, wear-resisting, thickness of coating is even, at the numerous areas of the industrial aspect such as machinery, electronics, petrochemical complex, mining, medicine equipment, automobile, aviation, is used widely.By in the coating that obtains of phosphorus chemistry nickel plating technology there is good solidity to corrosion, and in traditional nickel chemical plating technology stablizer, contain the heavy metal ion such as lead ion, brightening agent contains cadmium ion compound.These harmful heavy metals in traditional chemical nickel-plating waste water, although still the difficulty of wastewater treatment is very big less for addition, because dealing with improperly, it is accumulated in environment, will cause severe contamination to local environment, the impact that the character of heavy metal itself makes this pollution produce permanence, the injury that ecotope and human survival are caused is catastrophic.
In chemical nickel-plating solution, additive adds, not only can stop or postpone the Auto-decomposition of chemical nickel-plating solution, play the effect of stablizing plating solution, sometimes can also add fast response, improve phosphorus content and the internal stress of chemical Ni-plating layer, thereby, for a ripe electroless plating nickel product, the additive important component part that is absolutely necessary, but how traditional additive is containing heavy metals such as lead ions, is inevitably mingled with plumbous etc. to environment and the harmful heavy metal of human body in chemical nickel coating.Particularly in recent years, people require more and more higher to the bright property of chemical nickel, in order to obtain coating attractive in appearance, proposed to add the method for brightening agent in chemical nickel-plating solution, and relatively ripe using heavy metal lead, the cadmium ion of tradition can not meet people's requirement as the nickel chemical plating technology of stablizer and brightening agent, particularly product technology requires and environmental emission requirement.
Summary of the invention
The object of this invention is to provide phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type.
The technical solution used in the present invention is: phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type, it is comprised of A and two kinds of components of B, A component comprises the Nanometer Copper of the raw material of following concentration: 2-5mg/L and the mixture of soluble copper salt, the sulfuric acid rhenium of 2-4mg/L, 1-4mg/L sodium allyl sulfonate (ALS), complexing agent, stablizer, the NaOH of 20-40g/L; B component comprises the butynediol diethoxy ether (BEO) of the raw material of following concentration: 1-4mg/L, the N of 1-3mg/L, N-diethyl propargylamine (DEP), the BBI of 1-4mg/L (BBI), the sodium hydroxymethane sulfonate of 2-4mg/L (PN).
Described complexing agent is citric acid, lactic acid, propionic acid, DL-oxysuccinic acid, the mixture of succinic acid.
Described stablizer is tellurium dioxide, bismuth citrate, thiocarbamide, the mixture of Potassium Iodate.
Described soluble copper salt is copper sulfate, and in the mixture of nanometer copper and copper sulfate, the mass percent of copper sulfate is 50%-57%.
The content of each composition of complexing agent of the present invention is: citric acid 2.5-8g/L, lactic acid 12-70 g/L, propionic acid 5-40 g/L, DL-oxysuccinic acid 2-10 g/L, succinic acid 2-8 g/L.
Each component content of stablizer of the present invention is: tellurium dioxide 0.001-0.0017g/L, bismuth citrate 0.1-0.3g/L, thiocarbamide 0.3-0.5 g/L, Potassium Iodate 0.2-0.5 g/L.
Advantage of the present invention is: add and can make after this additive coating reach the effect of full light, and it is fast to go out ray velocity, general about 3 minutes start to be half light, within 10 minutes, just can reach mirror effect.And brightening agent consumption is few, plating solution remains stable state, and binding force of cladding material is good, the excellent corrosion resistance of coating, and with the test of nitric acid spot corrosion method, the time of resistance to nitric acid can reach more than 300 seconds.
The object of the present invention is to provide phosphorus chemistry nickel plating additive formulations in the high light of a kind of environment-friendly type, and obtain and to go out faster ray velocity, and coating has good minute surface brightness effect, bonding force is good, excellent corrosion resistance.
Embodiment
Phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type, it is comprised of A and two kinds of components of B, A component comprises the raw material of following concentration: the mixture of 2-5mg/L Nanometer Copper and soluble copper salt, the sulfuric acid rhenium of 2-4mg/L, 1-4mg/L sodium allyl sulfonate (ALS), complexing agent, stablizer, the NaOH of 20-40g/L; B component comprises the butynediol diethoxy ether (BEO) of the raw material of following concentration: 1-4mg/L, the N of 1-3mg/L, N-diethyl propargylamine (DEP), the BBI of 1-4mg/L (BBI), the sodium hydroxymethane sulfonate of 2-4mg/L (PN).
While preparing above-mentioned additive, Nanometer Copper, soluble copper salt, sulfuric acid rhenium, sodium allyl sulfonate (ALS), complexing agent, stablizer, NaOH are mixed together in and in water, form additive A, and butynediol diethoxy ether (BEO), N, N-diethyl propargylamine (DEP), BBI (BBI), sodium hydroxymethane sulfonate (PN) is mixed together in and in water, forms additive B, the method of additive application in chemical nickel-plating solution is: in each plating cycle, to the additive A and the B that add respectively 0.5-10mL in every liter of plating solution.
The working temperature of chemical nickel-plating solution is 88-92 ℃.
The pH scope of chemical nickel-plating solution is 4. 5-4. 9.
The plating loading capacity of chemical nickel-plating solution is 0. 5-2. 5 dm
2/ L.
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1.
Formula and operational condition are as follows: single nickel salt 20g/L, inferior sodium phosphate 25g/L, crystallization sodium acetate 12g/L, lactic acid l0ml/L, copper sulfate 1 mg/L, additive 8ml/L (additive A 4ml/L, additive B 4ml/L), the pH value of plating solution is 4.5, and loading capacity is 1dm
2/ L, plating temperature is 88-92 ℃, plating time is 10 minutes.
Preparation plating solution: the various medicines of above-mentioned calculated amount are measured by the volume integral another name of plating solution, then with deionized water, solid medicine is dissolved completely, thick liquid medicine is diluted to dilute solution.Will be first by single nickel salt and sodium acetate, lactic acid mixed dissolution, then mix with the ortho phosphorous acid sodium solution having dissolved, the amount of red-tape operati water, in 3/4 left and right of configuration liquor capacity, can not surpass prescribed volume.After finally adjusting pH value to 4.5 with 1:l ammoniacal liquor, be diluted to prescribed volume.
Test piece plating pre-treatment: electrochemical deoiling one flowing water cleans activation (1:1 hydrochloric acid) flowing water and cleans.
Plating: the plating solution preparing is put into thermostat water bath and be heated to 88 ℃, measure the additive solution having prepared with graduated cylinder, add successively in plating solution, adjust pH value, again the good iron-based test piece of pre-treatment is carried out to mark, in plating solution central mounting, the reaction times is 10 minutes.
Performance test: when the reaction times is 3 minutes, take out test piece, find that test piece has been half bright state, take out after 10 minutes, test piece coating almost can reach mirror effect, and brightness is excellent; With the salpeter solution preparing, measure its erosion resistance, the coating blackening time was over 300 seconds; 180 degree alternating bending test pieces five times, coating surface does not have peeling, decortication phenomenon.
Embodiment 2.
Formula and operational condition are as follows: single nickel salt 22g/L, inferior sodium phosphate 28g/L, crystallization sodium acetate 15g/L, lactic acid 8ml/L, copper sulfate 1 mg/L, additive 8ml/L (additive A 2ml/L, additive B 6ml/L), the pH value of plating solution is 4.7, and loading capacity is 1.5 dm
2/ L, plating temperature is 88-92 ℃, plating time is 10 minutes.
The preparation of plating solution: the various medicines of above-mentioned calculated amount are measured by the volume integral another name of plating solution, then with deionized water, solid medicine is dissolved completely, thick liquid medicine is diluted to dilute solution.Will be first by single nickel salt and sodium acetate, lactic acid mixed dissolution, then mix with the ortho phosphorous acid sodium solution having dissolved, the amount of red-tape operati water, in 3/4 left and right of configuration liquor capacity, can not surpass prescribed volume.After finally adjusting pH value to 4.7 with 1:l ammoniacal liquor, be diluted to prescribed volume.
Test piece plating pre-treatment: electrochemical deoiling one flowing water cleans activation (1:1 hydrochloric acid) flowing water and cleans.
Plating: the plating solution preparing is put into thermostat water bath and be heated to 88 ℃, measure the additive solution having prepared with graduated cylinder, add in plating solution successively.Adjust pH value, the better iron-based test piece of pre-treatment is carried out to mark, in plating solution central mounting, the reaction times is 10 minutes.
Performance test: when the reaction times is 3 minutes, take out test piece, find that test piece has been half bright state, take out after 10 minutes, test piece coating almost can reach mirror effect, and brightness is excellent; With the salpeter solution preparing, measure its erosion resistance, the coating blackening time surpasses 300 seconds, 180 degree alternating bending test pieces five times, and coating surface does not have peeling, decortication phenomenon.
Embodiment 3.
Formula and operational condition are as follows: single nickel salt 25g/L, inferior sodium phosphate 30g/L, crystallization sodium acetate 10g/L, lactic acid 5ml/L, copper sulfate 1 mg/L, additive 8ml/L (additive A 6ml/L, additive B 2ml/L), the pH value of plating solution is 4.9, and loading capacity is 2 dm
2/ L, plating temperature is 88-92 ℃, plating time is 10 minutes.
The preparation of plating solution: the various medicines of above-mentioned calculated amount are measured by the volume integral another name of plating solution, then with deionized water, solid medicine is dissolved completely, thick liquid medicine is diluted to dilute solution.Will be first by single nickel salt and sodium acetate, lactic acid mixed dissolution, then mix with the ortho phosphorous acid sodium solution having dissolved, the amount of red-tape operati water, in 3/4 left and right of configuration liquor capacity, can not surpass prescribed volume.After finally adjusting pH value to 4.9 with 1:l ammoniacal liquor, be diluted to prescribed volume.
Test piece plating pre-treatment: electrochemical deoiling one flowing water cleans activation (1:1 hydrochloric acid) flowing water and cleans.
Plating: the plating solution preparing is put into thermostat water bath and be heated to 88 ℃, measure the additive solution having prepared with graduated cylinder, add in plating solution successively.Adjust pH value, the better iron-based test piece of pre-treatment is carried out to mark, in plating solution central mounting, the reaction times is 10 minutes.
Performance test: when the reaction times is 3 minutes, take out test piece, find that test piece has been half bright state, take out after 10 minutes, test piece coating almost can reach mirror effect, and brightness is excellent; With the salpeter solution preparing, measure its erosion resistance, the coating blackening time was over 300 seconds; 180 degree alternating bending test pieces five times, coating surface does not have peeling, decortication phenomenon.
Claims (6)
1. phosphorus chemistry nickel plating additive in the high light of environment-friendly type, it is characterized in that: it is comprised of A and two kinds of components of B, A component comprises the Nanometer Copper of the raw material of following concentration: 2-5mg/L and the mixture of soluble copper salt, the sulfuric acid rhenium of 2-4mg/L, the sodium allyl sulfonate of 1-4mg/L (ALS), complexing agent, stablizer, the NaOH of 20-40g/L; B component comprises the butynediol diethoxy ether (BEO) of the raw material of following concentration: 1-4mg/L, the N of 1-3mg/L, N-diethyl propargylamine (DEP), the BBI of 1-4mg/L (BBI), the sodium hydroxymethane sulfonate of 2-4mg/L (PN).
2. phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type according to claim 1, is characterized in that: described complexing agent is citric acid lactic acid, propionic acid, DL-oxysuccinic acid, the mixture of succinic acid.
3. phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type according to claim 1, is characterized in that: described stablizer is tellurium dioxide bismuth citrate, thiocarbamide, the mixture of Potassium Iodate.
4. phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type according to claim 1, is characterized in that: soluble copper salt is copper sulfate, and in the mixture of nanometer copper and copper sulfate, the mass percent of copper sulfate is 50%-57%.
5. phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type according to claim 2, in complexing agent, the content of each composition is: citric acid 2.5-8g/L, lactic acid 12-70 g/L, propionic acid 5-40 g/L, DL-oxysuccinic acid 2-10 g/L, succinic acid 2-8 g/L.
6. phosphorus chemistry nickel plating additive in the high light of a kind of environment-friendly type according to claim 3, it is characterized in that: in stablizer, the content of each composition is: tellurium dioxide 0.001-0.0017g/L, bismuth citrate 0.1-0.3g/L, thiocarbamide 0.3-0.5 g/L, Potassium Iodate 0.2-0.5 g/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039940A (en) * | 2015-07-13 | 2015-11-11 | 宁波市鄞州双诺机械有限公司 | Nickel plating method for bearing cap |
| CN108251825A (en) * | 2018-04-12 | 2018-07-06 | 朱玉兰 | It is a kind of to plate the fast iron oxygen magnetic core chemical nickel-plating solution of speed |
| CN108728833A (en) * | 2018-08-24 | 2018-11-02 | 朱玉兰 | A kind of high rigidity chemical nickel-plating solution and its chemical plating process for aluminium alloy |
| CN109609936A (en) * | 2018-12-26 | 2019-04-12 | 江南大学 | A kind of self-catalysis alloy layer |
| CN113802114A (en) * | 2021-09-16 | 2021-12-17 | 深圳市大正瑞地科技有限公司 | Lead-free environment-friendly chemical nickel solution and chemical nickel plating process using same |
| CN114411129A (en) * | 2021-12-29 | 2022-04-29 | 广东利尔化学有限公司 | Environment-friendly high-phosphorus nickel plating additive |
| CN115418631A (en) * | 2022-09-05 | 2022-12-02 | 吉安宏达秋科技有限公司 | Environment-friendly bright medium-phosphorus chemical nickel plating solution and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104561948B (en) * | 2015-01-28 | 2015-08-05 | 哈尔滨三泳金属表面技术有限公司 | A kind of environment-friendly type aluminium alloy rapid chemical nickel plating-phosphorus additive |
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| CN101638778A (en) * | 2009-02-27 | 2010-02-03 | 郑建国 | Nickel-phosphorus chemical precipitation plating layer of aluminium alloy |
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| CN101638778A (en) * | 2009-02-27 | 2010-02-03 | 郑建国 | Nickel-phosphorus chemical precipitation plating layer of aluminium alloy |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039940A (en) * | 2015-07-13 | 2015-11-11 | 宁波市鄞州双诺机械有限公司 | Nickel plating method for bearing cap |
| CN105039940B (en) * | 2015-07-13 | 2017-12-01 | 宁波市鄞州双诺机械有限公司 | A kind of nickel plating process of bearing cap |
| CN108251825A (en) * | 2018-04-12 | 2018-07-06 | 朱玉兰 | It is a kind of to plate the fast iron oxygen magnetic core chemical nickel-plating solution of speed |
| CN108728833A (en) * | 2018-08-24 | 2018-11-02 | 朱玉兰 | A kind of high rigidity chemical nickel-plating solution and its chemical plating process for aluminium alloy |
| CN109609936A (en) * | 2018-12-26 | 2019-04-12 | 江南大学 | A kind of self-catalysis alloy layer |
| CN113802114A (en) * | 2021-09-16 | 2021-12-17 | 深圳市大正瑞地科技有限公司 | Lead-free environment-friendly chemical nickel solution and chemical nickel plating process using same |
| CN113802114B (en) * | 2021-09-16 | 2024-02-02 | 深圳市大正瑞地科技有限公司 | Lead-free environment-friendly chemical nickel solution and chemical nickel plating process using same |
| CN114411129A (en) * | 2021-12-29 | 2022-04-29 | 广东利尔化学有限公司 | Environment-friendly high-phosphorus nickel plating additive |
| CN115418631A (en) * | 2022-09-05 | 2022-12-02 | 吉安宏达秋科技有限公司 | Environment-friendly bright medium-phosphorus chemical nickel plating solution and application thereof |
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| CN103726036B (en) | 2015-01-07 |
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