CN103334095B - A kind of chemical nickel-plating liquid and application thereof - Google Patents
A kind of chemical nickel-plating liquid and application thereof Download PDFInfo
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- CN103334095B CN103334095B CN201210387986.3A CN201210387986A CN103334095B CN 103334095 B CN103334095 B CN 103334095B CN 201210387986 A CN201210387986 A CN 201210387986A CN 103334095 B CN103334095 B CN 103334095B
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Abstract
The open a kind of chemical nickel-plating liquid of the present invention, is made up of the distilled water of 30g nickel sulfate, 30g sodium hypophosphite, 20g sodium acetate, 20g sodium citrate, 1～5g additive and surplus by every liter of calculating, and described additive is soluble in water, and its molecular formula is CnHpXm.When a kind of chemical nickel-plating liquid of the present invention achieves 30 50 DEG C of platings of low temperature, the sedimentation rate of chemical nickel-plating solution keeps constant, and in Ni P alloy layer, the content of P can reach 9.31 (wt) % 15.80 (wt) %；During middle 60 75 DEG C of platings of temperature, the sedimentation rate of chemical nickel-plating solution can be improved, the content of P in Ni P alloy layer can be made again to reach 9.39 (wt) % 12.90 (wt) %.Meanwhile, in the case of Ni P alloy layer thickness reduces, the corrosion resisting property of coating is greatly improved.
Description
Technical field
The present invention relates to a kind of electroplate liquid, particularly to a kind of chemical-electrical nickel-plating liquid and answering in nickel process thereof
With.
Background technology
The wearability of Electroless Ni-P Alloy Coating, corrosion resistance, solderability are excellent, coating has hardness height and electromagnetic shielding performance
Characteristic, and thickness of coating is uniform, is applicable to the plating of various material (including nonmetallic materials) complex parts, navigates in space flight
The aspects such as sky, petrochemical industry, electronics industry, transportation, IT industry are widely used.
At present, the usual Sodium Hypophosphite of acidic electroless Ni-P plating technique is as reducing agent, and plating temperature is generally higher
Carry out at temperature i.e. 85-95 DEG C.When bath temperature height, although acid chemical plating nickel liquor deposition velocity is fast, but high temperature pair
Coating bath and firing equipment require higher, and energy consumption is big, and plating solution is volatile, and bath stability is poor, and the utilization rate of hypophosphite is low, with
Time bring the difficulty of technology controlling and process and maintenance；It addition, the at high temperature plating of acid chemical plating nickel liquid is to some material such as plastics etc.
Deformation and the modification of matrix can be caused.
List of references
[1] Liu Yongjian, Wang Yinpei. Electroless Nickel Deposition In Sodium Hypophosphite-based Bath Depositing Mechanism [J]. East China University of Science is learned
Report, 2001,27 (3): 301-306
[2] Zhang Zhaolan, Zhang Bo, a waterside etc. the research of low temperature chemcial plating nickel and application [J] thereof. Shaanxi Normal University's journal,
1998,26(4):71-73
[3] Chen Keming, Chen Yuqiu, Qiao Xueliang etc. LOW TEMPERATURE ELECTROLESS NICKEL PLATING PROCESS [J]. plating and environmental protection, 1996,16 (3):
15-17
[4] Huang Yueshan, covers dragon of continuing, Li Yi etc. the research [J] of LOW TEMPERATURE ELECTROLESS NICKEL PLATING PROCESS. and plating and environmental protection, 1998,2:
18-20
[5] Li Jiansan, Li Yi, Liao Jing give pleasure to. the research [J] of LOW TEMPERATURE ELECTROLESS NICKEL PLATING PROCESS and coating performance. and the new work of new technique
Skill .2002,37-39
[6] Ou Yangxinping, Luo Haojiang. low temperature chemcial plating nickel progress [J]. plating and finish, 2000,19 (3): 42-
45
[7] Zhang Pijian, Liu Yanhong, Xia Zhenzhan. the research [J] of low temperature High Speed Electroless Nickel Plating. plating and environmental protection,
2005,25(2):24-26
[8] Wang Yong, Zeng Zhenou, Zhang Xiaoming etc. the research [J] of middle temperature high phosphorus chemical plating nickel accelerator. electroplate and cover with paint, lacquer, colour wash, etc., 29
(12):25-28
[9] Cao Chunan. corrosion electrochemistry principle (third edition) [M]. Beijing: Chemical Industry Press, 2008
[10] Liu Yonghui. Electrochemical Measurement Technology [M]. Beijing: publishing house of Beijing Aeronaution College, 1992
Summary of the invention
An object of the present invention provides a kind of chemical nickel-plating liquid to solve above-mentioned technical problem.
The two of the purpose of the present invention are to provide above-mentioned a kind of chemical nickel-plating liquid answering in a kind of nickel process
With.
Technical scheme
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is soluble in water, and its structure is CnHpXm, during wherein X is O, N and S one or more
Atom, wherein m=1-3, n=1-7, p=1-7；C atom and X atom presented in-C=X key, and between X atom with-
X-X-or-X=X-key-like becomes.
The preparation method of above-mentioned a kind of chemical nickel-plating liquid, nickel sulfate, sodium acetate, sodium citrate will be dissolved in distilled water
In and stir, then sodium hypophosphite and additive are dissolved in wherein and will mix uniformly, then with sulphuric acid, pH value is adjusted
After 5.1, obtain chemical nickel-plating liquid.
Above-mentioned a kind of chemical nickel-plating liquid when chemical nickel plating, useful load≤2.5dm2/ L, plating temperature be 30-50 DEG C or
60-75 DEG C, plating time 30-60min.
Beneficial effects of the present invention
A kind of chemical nickel-plating liquid of the present invention, i.e. on the basis of existing electroless plating technology formula, uses interpolation difference to contain
The additive of amount, it is achieved that under cryogenic conditions during i.e. 30-50 DEG C of plating, the sedimentation rate of chemical nickel-plating solution with without additive
Base soln keep constant, and in Ni-P alloy layer, the content of P can reach 9.31 (wt) %-15.80 (wt) %.I.e. with
Prior art compares, it is possible to achieve high corrosion-resistant, the deposition of non magnetic Ni-P alloy under cryogenic conditions, and decreases plating solution
Volatilization, plating improves the stability of plating solution and adds the utilization rate of sodium hypophosphite in plating solution.
Further, a kind of chemical nickel-plating liquid of the present invention, the most i.e. during 60-75 DEG C of plating, can raising
Learn the sedimentation rate of nickel plating solution, the content of P in Ni-P alloy layer can be made again to reach 9.39 (wt) %-12.90 (wt) %.I.e.
While increasing or keeping plating solution deposition velocity, the most not only reduce the plating temperature of plating solution, carry again simultaneously
The utilization rate of sodium hypophosphite in P content, the stability that improve plating solution and plating solution in high alloy layer, it is achieved that medium temperature condition
Under the deposition of non magnetic Ni-P alloy, particularly in preferred embodiment 8, show in the feelings that Ni-P alloy layer thickness reduces
Under condition, the corrosion resisting property of coating is greatly improved.
Accompanying drawing explanation
Fig. 1 a, embodiment 1 gained Ni-P alloy layer SEM figure；
Fig. 1 b, embodiment 1 gained Ni-P alloy layer EDS figure；
Fig. 2 a, embodiment 1 gained Ni-P alloy layer SEM figure；
Fig. 2 b, embodiment 1 gained Ni-P alloy layer EDS figure；
Fig. 3 a, embodiment 1 gained Ni-P alloy layer SEM figure；
Fig. 3 b, embodiment 1 gained Ni-P alloy layer EDS figure；
Fig. 4 a, embodiment 1 gained Ni-P alloy layer SEM figure；
Fig. 4 b, embodiment 2 gained Ni-P alloy layer EDS figure；
Fig. 5 a, embodiment 3 gained Ni-P alloy layer SEM figure；
Fig. 5 b, embodiment 4 gained Ni-P alloy layer EDS figure；
Fig. 6 a, embodiment 5 gained Ni-P alloy layer SEM figure；
Fig. 6 b, embodiment 6 gained Ni-P alloy layer EDS figure；
Fig. 7 a, embodiment 7 gained Ni-P alloy layer SEM figure；
Fig. 7 b, embodiment 7 gained Ni-P alloy layer EDS figure；
Fig. 8 a, the polarization curve of Ni-P alloy layer of embodiment 8 gained；
Fig. 8 b, the polarization curve of Ni-P alloy layer of embodiment 8 gained.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is expanded on further, but it is not limiting as the present invention.
Reagent used by the present invention
Nickel sulfate (NiSO4·6H2O), sodium hypophosphite (NaH2PO2·H2O), sodium citrate (C6H5Na3O7·2H2O), vinegar
Acid sodium (C2H3NaO2), concentrated sulphuric acid (H2SO4) above reagent is commercially available analytical reagent.
Test instrunment used by the present invention:
FDAC 3400N scanning electron microscope, Germany's BrukerQUANTAX energy depressive spectroscopy；
Germany's Fischer company XMDVM-T7.1-w thickness of coating tester；
Autolab PG-STAT302 electrochemical workstation.
Coating decay resistance is tested
Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, after distilled water cleans up, put into constant temperature 60 DEG C
The chemical nickel-plating solution containing 1g/L additive in plating 30min；Plating complete taking-up sample, distilled water clean coating and use
Cold wind dries up.
Then using Autolab PG-STAT302 electrochemical workstation, Ni-P alloy layer sample is working electrode (S=
1cm2), auxiliary electrode is the platinum electrode being coated with platinum black, and reference electrode is saturated calomel electrode (SCE)；Temperature be 25 DEG C, molten
Solve in oxygen-saturated 3.5%NaCl electrolyte solution and measure polarization curve respectively.
The sedimentation rate of indication of the present invention refers to the thickness of Ni-P alloy deposition layer in the 60min time.
Embodiment 1
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is soluble in water, its molecular formula be CnHpXm, i.e. X be O, N and S atom, wherein m=4, n=7, p
=5；C atom and X atom are presented in-C=X key, and become with-X-X-or-X=X-key-like between X atom, i.e. described
Additive is a kind of heteroaromatic class organic compound, ripe entitled saccharin, and its structural formula is as follows:
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 1g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Utilizing above-mentioned a kind of chemical nickel-plating liquid that cold-rolled carbon steel is carried out plating, specific operation process is as follows:
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 30 DEG C
Water-bath in heating and constant temperature；
Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, after distilled water cleans up, put into constant temperature 30 DEG C
Chemical nickel-plating solution in plating 60min；
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, with Germany Fischer company XMDVM-
Thickness and the plating of coating measured respectively by T7.1-W type X-ray thickness gauge and Germany's Bruker company QUANTAX type EDS analyser
The content of P in Ceng.
Wherein thickness of coating is the meansigma methods of 5-6 difference measured value, and measurement result display thickness of coating is 0.52 μm,
In coating, the content of P is 10.66 (wt) %, compares, Essential Chemistry nickel plating solution (identical chemical composition and operating condition, but
It being added without additive) the later thickness of coating of plating is that in 0.6 μm and coating, P content is 6.63 (wt) %, thus can obtain
Go out to add a kind of chemical nickel-plating solution of the present invention after additive, although its sedimentation rate keeps constant, and Ni-P alloy
In coating, the content of P substantially increases.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 1a, can be seen that Ni-P alloy deposition layer covers base from Fig. 1 a
Body metal surface, the surface topography of coating is more or less the same with the surface topography of parent metal, shows that thickness of coating is relatively thin.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 1 b, can obtain the weight of Ni and P element in coating and contain from Fig. 1 b
Amount and atom content, as shown in the table.
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 10.66 | 18.44 | 0.3 |
| Ni | 89.34 | 81.56 | 1.4 |
As can be seen from the above table, after the chemical nickel-plating liquid plating of the use present invention, in the Ni-P alloy layer of gained, Ni is first
The content of element is 89.34 (wt) %, and the content of P element is 10.66 (wt) %.
Embodiment 2
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 1；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 5g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Utilizing above-mentioned a kind of chemical nickel-plating liquid that cold-rolled carbon steel is carried out plating, specific operation process is as follows:
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 30 DEG C
Water-bath in heating and constant temperature；
Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, after distilled water cleans up, put into constant temperature 30 DEG C
Chemical nickel-plating solution in plating 60min；
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, with Fischer company of Germany
XMDVM-T7.1-W type X-ray thickness gauge and Germany's Bruker company QUANTAX type EDS analyser are measured respectively
The content of P in the thickness of coating and coating.
Wherein thickness of coating is the meansigma methods of 5-6 difference measured value, and measurement result display thickness of coating is 0.6 μm,
In coating, the content of P is 12.72 (wt) %, compares, Essential Chemistry nickel plating solution (identical chemical composition and operating condition, but
It being added without additive) the later thickness of coating of plating is that in 0.6 μm and coating, P content is 6.63 (wt) %, thus can obtain
Go out to add a kind of chemical nickel-plating solution of the present invention after additive, although its sedimentation rate keeps constant, and Ni-P alloy
In coating, the content of P substantially increases.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and obtains weight content and the atom content of Ni and P element in coating, as shown in the table.
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 12.72 | 21.63 | 0.3 |
| Ni | 87.28 | 78.37 | 1.3 |
As can be seen from the above table, after the chemical nickel-plating liquid plating of the use present invention, in the Ni-P alloy layer of gained, Ni is first
The content of element is 87.28 (wt) %, and the content of P element is 12.72 (wt) %.
Embodiment 3
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 1；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 3g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Utilizing above-mentioned a kind of chemical nickel-plating liquid that cold-rolled carbon steel is carried out plating, specific operation process is as follows:
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 30 DEG C
Water-bath in heating and constant temperature；
Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, after distilled water cleans up, put into constant temperature 30 DEG C
Chemical nickel-plating solution in plating 60min；
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, with Fischer company of Germany
XMDVM-T7.1-W type X-ray thickness gauge and Germany's Bruker company QUANTAX type EDS analyser are measured respectively
The content of P in the thickness of coating and coating.
Wherein thickness of coating is the meansigma methods of 5-6 difference measured value, and measurement result display thickness of coating is 0.58 μm,
In coating, the content of P is 11.42 (wt) %, compares, Essential Chemistry nickel plating solution (identical chemical composition and operating condition, but
It being added without additive) the later thickness of coating of plating is that in 0.6 μm and coating, P content is 6.63 (wt) %, thus can obtain
Go out to add a kind of chemical nickel-plating solution of the present invention after additive, although its sedimentation rate keeps constant, and Ni-P alloy
In coating, the content of P substantially increases.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and obtains weight content and the atom content of Ni and P element in coating, as shown in the table.
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 11.42 | 19.65 | 0.3 |
| Ni | 88.58 | 80.38 | 1.3 |
As can be seen from the above table, after the chemical nickel-plating liquid plating of the use present invention, in the Ni-P alloy layer of gained, Ni is first
The content of element is 88.58 (wt) %, and the content of P element is 11.42 (wt) %.
Embodiment 4
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is soluble in water, its molecular formula be CnHpXm, i.e. X be O and atom N, wherein m=3, n=1, p=
4；C atom and X atom are presented in-C-X or-C=X key, and become with-X-X-key-like between X atom, i.e. described interpolation
Agent is a kind of amine organic compound containing N, O, ripe entitled carbamide,
Its structural formula is as follows:
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 5g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 30 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 30 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure coating respectively with test instrunment
The content of P in thickness and coating, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display coating
Thickness is 0.61 μm, and in coating, the content of P is 12.23 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and
Operating condition, but be added without additive) content (6.63 of P in the later thickness of coating (0.6u) of plating and coating
(wt) %), it will be apparent that drawing the chemical nickel-plating solution after adding additive, its sedimentation rate keeps constant, and Ni-P alloy
In coating, the content of P substantially increases.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 2 a, can be seen that Ni-P alloy deposition layer covers base from Fig. 2 a
Body metal surface, the surface topography of coating is more or less the same with the surface topography of parent metal, shows that thickness of coating is relatively thin, and coating
There is seminess.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 2 b, can obtain the weight of Ni and P element in coating and contain from Fig. 2 b
Amount and atom content, as shown in the table.
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 12.23 | 20.88 | 0.4 |
| Ni | 87.77 | 79.12 | 1.7 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 87.77 (wt) %, and the content of P element is 12.23 (wt) %.
Embodiment 5
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 2；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 5g additive are dissolved in wherein and will mix uniformly；Then the dilute sulfuric acid with 10% will
PH value is adjusted to 5.1, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 40 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 50 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, with Germany Fischer company XMDVM-
T7.1-w thickness of coating tester and Germany's BrukerQUANTAX energy depressive spectroscopy measure P in the thickness of coating and coating respectively
Content, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display thickness of coating be 1.27 μm,
In coating, the content of P is 15.80 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and operating condition, but not
Add additive) content (11.07 (wt) %) of P in the later thickness of coating (1.27 μm) of plating and coating, it will be apparent that
Going out to add the chemical nickel-plating solution after additive, its sedimentation rate keeps constant, and in Ni-P alloy layer, the content of P is obvious
Increase..
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 3 a, can be seen that Ni-P alloy layer is evenly distributed from Fig. 3 a, plating
Layer surface is more smooth.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 3 b, can obtain the weight of Ni and P element in coating and contain from Fig. 3 b
Amount and atom content, as shown in the table:
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 15.80 | 26.22 | 0.6 |
| Ni | 84.20 | 73.78 | 1.7 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 84.20 (wt) %, and the content of P element is 15.80 (wt) %.
Embodiment 6
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 2；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 5g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 60 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 60 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure coating respectively with test instrunment
The content of P in thickness and coating, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display coating
Thickness is 4.34 μm, and in coating, the content of P is 12.90 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and
Operating condition, but be added without additive) content (8.08 of P in the later thickness of coating (4.27 μm) of plating and coating
(wt) %), it will be apparent that drawing the chemical nickel-plating solution after adding additive, its sedimentation rate increases, and Ni-P alloy
In coating, the content of P substantially increases.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in fig. 4 a, can be seen that Ni-P alloy layer surfacing from Fig. 4 a, plating
Layer is evenly distributed, and coating is without crystal boundary.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 4 b, can obtain Ni and the weight of P element in coating from Fig. 4 b
Content and atom content, as shown in the table:
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 12.90 | 21.92 | 0.5 |
| Ni | 87.10 | 78.08 | 2.4 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 87.10 (wt) %, and the content of P element is 12.90 (wt) %.
Embodiment 7
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 1；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 5g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 65 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 65 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure coating respectively with test instrunment
The content of P in thickness and coating, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display coating
Thickness is 4.44 μm, and in coating, the content of P is 12.21 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and
Operating condition, but be added without additive) content (11.69 of P in the later thickness of coating (4.58 μm) of plating and coating
(wt) %), it will be apparent that drawing the chemical nickel-plating solution after adding additive, its sedimentation rate is kept essentially constant, and Ni-
In P alloy layer, the content of P substantially increases.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 5 a, can be seen that Ni-P alloy layer surfacing from Fig. 5 a, plating
Layer is evenly distributed, and coating is without crystal boundary.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 5 b, can obtain Ni and the weight of P element in coating from Fig. 5 b
Content and atom content, as shown in the table:
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 12.21 | 20.86 | 0.3 |
| Ni | 87.79 | 79.14 | 1.3 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 87.79 (wt) %, and the content of P element is 12.21 (wt) %.
Embodiment 8
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 1；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 1g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 70 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 70 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure coating respectively with test instrunment
The content of P in thickness and coating, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display coating
Thickness is 7.26 μm, and in coating, the content of P is 11.69 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and
Operating condition, but be added without additive) content (12.23 of P in the later thickness of coating (5.86 μm) of plating and coating
(wt) %), it will be apparent that drawing the chemical nickel-plating solution after adding additive, its sedimentation rate significantly improves, and Ni-P alloy
In coating, the content of P is basically unchanged.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 6 a, can be seen that Ni-P alloy layer surfacing from Fig. 6 a, plating
Layer is evenly distributed, and coating is without crystal boundary and has fine and close micro-crack.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 6 b, can obtain Ni and the weight of P element in coating from Fig. 6 b
Content and atom content, as shown in the table:
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 11.69 | 20.06 | 0.4 |
| Ni | 88.31 | 79.94 | 1.7 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 88.31 (wt) %, and the content of P element is 11.69 (wt) %.
Embodiment 9
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 1；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 1g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 75 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 60min in the chemical nickel-plating solution of constant temperature 75 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure coating respectively with test instrunment
The content of P in thickness and coating, wherein thickness of coating is the meansigma methods of 5-6 difference measured value, measurement result display coating
Thickness is 9.39 μm, and in coating, the content of P is 12.31 (wt) %, the Essential Chemistry that compares nickel plating solution (identical chemical composition and
Operating condition, but be added without additive) content (12.35 of P in the later thickness of coating (2.25 μm) of plating and coating
(wt) %), it will be apparent that drawing the chemical nickel-plating solution after adding additive, its sedimentation rate significantly improves, and Ni-P alloy
In coating, the content of P keeps constant.
After a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, the coating of gained, is scanned by FDAC 3400N
Electronic Speculum is scanned, its SEM surface topography, as shown in Figure 7a, can be seen that Ni-P alloy layer surfacing from Fig. 7 a, plating
Layer is evenly distributed, and coating is without crystal boundary.
The coating of gained after a kind of chemical nickel-plating liquid plating of the above-mentioned employing present invention, by Germany BrukerQUANTAX
Energy depressive spectroscopy is measured, and its EDS schemes as shown in Figure 7b, can obtain Ni and the weight of P element in coating from Fig. 7 b
Content and atom content, as shown in the table:
| Element | Weight content [wt.%] | Atom content [at.%] | Error [%] |
| P | 12.31 | 21.01 | 0.4 |
| Ni | 87.69 | 78.99 | 1.8 |
As can be seen from the above table, the containing of Ni element in Ni-P alloy layer after using the chemical nickel-plating liquid plating of the present invention
Amount is 87.69 (wt) %, and the content of P element is 12.31 (wt) %.
Embodiment 10
A kind of chemical nickel-plating liquid, Sodium Hypophosphite be reducing agent, sodium citrate be chelating agent, on the basis of regular convention formula
By adding additive, its composition and content are as follows:
Described additive is with embodiment 2；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid is as follows:
By nickel sulfate 30g, sodium acetate 20g, sodium citrate 20g, it is dissolved in the beaker filling 500-700ml distilled water also
Stir, then 30g sodium hypophosphite and 1g additive are dissolved in wherein and will mix uniformly；Then it is 10% by volume ratio
PH value is adjusted to 5.1 by dilute sulfuric acid, then with distilled water, solution is diluted to 1L, obtains chemical nickel-plating liquid.
Measure in above-mentioned chemical nickel-plating solution 300ml to the 500ml beaker prepared with graduated cylinder, be then placed in constant temperature 60 DEG C
Water-bath in heating and constant temperature.Take cold-rolled carbon steel sheet 200# liquid honing thick for 1mm uniformly, distilled water cleans up
After, put into plating 30min in the chemical nickel-plating solution of constant temperature 60 DEG C.
Plating complete taking-up sample, distilled water clean coating and dry up with cold wind, measure the thickness of coating with test instrunment,
Wherein thickness of coating is the meansigma methods of 5-6 difference measured value, and measurement result display thickness of coating is 1.64 μm, and basisization
The thickness of coating learning nickel plating solution (identical chemical composition and operating condition, but be added without additive) plating later is 2.11 μm.
Then using Autolab PG-STAT302 electrochemical workstation, Ni-P alloy layer sample is working electrode (S=
1cm2), auxiliary electrode is the platinum electrode being coated with platinum black, and reference electrode is saturated calomel electrode (SCE)；Temperature be 25 DEG C, molten
Solve in oxygen-saturated 3.5%NaCl electrolyte solution and measure polarization curve respectively, as shown in Fig. 8 a, 8b.According to Fig. 8 a and Fig. 8 b
Middle polarization curve, utilizes Tafel polarization curve extrapolation (list of references [9], [10]) to draw additive chemistry nickel-plating liquid
The corrosion electricity of (i.e. basal liquid+1g/L additive in table) and Essential Chemistry nickel-plating liquid (i.e. basal liquid in table 1) coating sample
Position and corrosion rate are as shown in table 1
Table 1, corrosion of coating electromotive force and corrosion current
Be can be seen that by table 1, Essential Chemistry nickel plating solution (i.e. basal liquid in table 1) adds additive (i.e. in table
Basal liquid+1g/L additive) plating later, Ni-P alloy layer thickness reduce and coating in phosphorus content improve situation
Under, the corrosion rate of coating is by 2.184uA/cm2Drop to 1.148uA/cm2, show that the corrosion resisting property of coating has bigger proposing
High.
In sum, a kind of Sodium Hypophosphite of the present invention be reducing agent, sodium citrate be chelating agent, at regular convention formula
On the basis of by adding additive, it is achieved that a kind of in, under cryogenic conditions, the deposition speed of chemical nickel-plating solution can be improved
Rate, can make again the content of P in Ni-P alloy layer reach the acid chemical plating nickel technique of raising, simultaneously, it is thus achieved that coating uniformly, cause
Close, excellent corrosion resistance.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and modification, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (3)
1. a chemical nickel-plating liquid, it is characterised in that its composition and content are as follows:
Nickel sulfate 30g/L
Sodium hypophosphite 30g/L
Sodium acetate 20g/L
Sodium citrate 20g/L
Additive 1～5g/L
Surplus is distilled water；
Described additive is carbamide or saccharin；
The preparation method of above-mentioned a kind of chemical nickel-plating liquid, is i.e. dissolved in distillation by nickel sulfate, sodium acetate, sodium citrate under room temperature
In water and stir, then sodium hypophosphite and additive it is dissolved in wherein and stirs, then with sulphuric acid, pH value being adjusted
Whole after 5.1, obtain a kind of chemical nickel-plating liquid.
2. a kind of chemical nickel-plating liquid as claimed in claim 1, it is characterised in that the sulphuric acid described in its preparation method is volume
Than the dilute sulfuric acid being 10%.
A kind of chemical nickel-plating liquid the most as claimed in claim 1 application in nickel process, it is characterised in that useful load
≤2.5dm2/ L, plating time 30-60min, plating temperature is 30-50 DEG C or 60-75 DEG C.
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| CN1404175A (en) * | 2002-09-16 | 2003-03-19 | 华南师范大学 | Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface of cog structure |
| CN1609271A (en) * | 2004-09-20 | 2005-04-27 | 东南大学 | Nickel phosphorus chemical plating method and chemical plating solution thereof |
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