CN110318045A - A kind of high stability chemical nickel-plating liquid and preparation method thereof - Google Patents
A kind of high stability chemical nickel-plating liquid and preparation method thereof Download PDFInfo
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- CN110318045A CN110318045A CN201910535132.7A CN201910535132A CN110318045A CN 110318045 A CN110318045 A CN 110318045A CN 201910535132 A CN201910535132 A CN 201910535132A CN 110318045 A CN110318045 A CN 110318045A
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- nickel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Abstract
This application involves chemical plating fields, and in particular to a kind of high stability chemical nickel-plating liquid and preparation method thereof.The invention discloses a kind of high stability chemical nickel-plating liquid, the component comprising following levels: 12~30g/L of complexing agent, 18~30g/L of nickel salt, 30~40g/L of reducing agent, 1~4g/L of buffer, 8~18ppm of stabilizer, wherein, the complexing agent includes oxalic acid, citric acid, propionic acid.The present invention is acted synergistically by multiple components, enhances the stability of plating solution, significantly improves the porosity of coating and simple, at low cost, the suitable industrialized production of present invention process.
Description
Technical field
The present invention relates to chemical plating fields, and in particular to a kind of high stability chemical nickel-plating liquid and preparation method thereof.
Background technique
Chemical plating is also known as electroless plating (Electroless plating), is referred to as self-catalysis plating
(Autocatalytic plating).Detailed process refers to: under certain condition, the metal ion in aqueous solution is reduced agent
Reduction, and the process being deposited on solid matrix surface.The basic principle of chemical nickel plating is: in the catalytic action of catalyst
Under, the hypophosphorous acid root in solution forms active hydride in catalytic surface catalytic dehydrogenation, and is oxidized to orthophosphite；Activity
Nickel ion in hydride and solution carries out reduction reaction and deposits nickel, hydrogen itself is oxidized to, at the same time, in solution
Part hypophosphorous acid root be hydrogenated object be reduced into it is elemental phosphorous enter coating.
Chemical nickel-plating liquid is widely used each industrial circle.Such as aerospace, it is repaired using chemical plating nickel technology
Multiple aircarft engine parts, auto industry, nickel plating, chemical work on the complex-shaped part such as gear, radiator and atomizer
Industry, inner wall protection, petroleum gas, food processing industry, mining industry, war industry, the electronic computer of large-scale reaction vessel
Deng.
But there is also many deficiencies in use for existing plating solution, and such as: (1) stability undesirable, and plating solution is easy
It decomposes；(2) resistance to corrosion of coating is poor；(3) coating is loose, porosity is larger.Due to the cost and ring of chemical plating
Guarantor's problem, the research focus of chemical plating is the stability problem of plating solution at present.Long-life chemical plating fluid not only can save the cost, and
And also help environmental protection, but the research of long-life plating solution have it is more highly difficult because the service life of plating solution and deposition rate are contradiction
, often the service life of plating solution extends, and deposition velocity is decreased obviously.
Summary of the invention
In order to solve the above technical problems, the first aspect of the present invention provides a kind of high stability chemical nickel-plating liquid, include
The component of following levels: 12~30g/L of complexing agent, 18~30g/L of nickel salt, 30~40g/L of reducing agent, 1~4g/ of buffer
L, 8~18ppm of stabilizer,
Wherein, the complexing agent includes oxalic acid, citric acid, propionic acid.
As a kind of perferred technical scheme, the reducing agent includes sodium hypophosphite, sodium borohydride, alkyl amine borine, hydrazine
At least one of.
As a kind of perferred technical scheme, the reducing agent is sodium hypophosphite.
As a kind of perferred technical scheme, the nickel salt include nickel sulfate, it is nickel chloride, nickel acetate, nickel sulfamic acid, secondary
At least one of nickel phosphate.
As a kind of perferred technical scheme, the nickel salt is nickel acetate.
As a kind of perferred technical scheme, the nickel-plating liquid further includes the component of following levels: auxiliary agent 80~
120ppm。
As a kind of perferred technical scheme, the auxiliary agent includes succinate sodium salt, neopelex, 12
At least one of sodium alkyl sulfate.
As a kind of perferred technical scheme, the auxiliary agent is lauryl sodium sulfate.
The second aspect of the present invention provides the preparation method of the chemical nickel-plating liquid, comprising the following steps:
(1) deionized water that prewired plating solution volume fraction is 50% is added at room temperature；
(2) then complexing agent, nickel salt, buffer is sequentially added under agitation to stir to whole dissolutions,
(3) remaining ionized water is added, reducing agent, stabilizer, auxiliary agent is added and stirs to whole dissolutions；Again with sulfuric acid tune
Save pH value be 4.1-5.0 to get.
The third aspect of the present invention provides a kind of nickel plating product, by impregnating workpiece to be plated in the nickel-plating liquid with shape
It is prepared at the mode of plated film.
The utility model has the advantages that the present invention is acted synergistically by multiple components, the stability of plating solution is enhanced, is significantly improved
Simple, at low cost, the suitable industrialized production of the porosity and present invention process of coating.
Detailed description of the invention
Fig. 1 is that the SEM of 8 nickel coating of the embodiment of the present invention schemes.
Specific embodiment
To solve the above-mentioned problems, the present invention provides a kind of high stability chemical nickel-plating liquids, include following levels
Component: 12~30g/L of complexing agent, 18~30g/L of nickel salt, 30~40g/L of reducing agent, 1~4g/L of buffer, stabilizer 8~
18ppm。
As a preferred embodiment, the chemical nickel-plating liquid, the component comprising following levels: complexing agent
18g/L, nickel salt 20g/L, reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm.
As a preferred embodiment, the chemical nickel-plating liquid, further includes the component of following levels: auxiliary agent 80
~120ppm.
It is highly preferred that the auxiliary agent 108ppm.
Unit ppm refers to mg/L.
Nickel salt
The nickel salt provides required Ni during electroless plating reaction2+。
As a preferred embodiment, the nickel salt include nickel sulfate, it is nickel chloride, nickel acetate, nickel sulfamic acid, secondary
At least one of nickel phosphate.
As a preferred embodiment, the nickel salt is nickel acetate.
Applicants have discovered that nickel acetate is selected to do main salt, the chloride ion that can reduce corrosion resistance of coating will not be generated, and not
Tensile stress can be generated.
Reducing agent
Reducing agent is added in nickel-plating liquid and restores Ni2+It is deposited on workpiece to be plated for Ni, reducing agent structure described herein
It is upper to contain two or more reactive hydrogens.
Reducing agent described herein includes at least one of sodium hypophosphite, sodium borohydride, alkyl amine borine, hydrazine.
As a preferred embodiment, the reducing agent is sodium hypophosphite.
Applicants have discovered that the reducing agent obtains Ni-P coating when being sodium hypophosphite, the content of P is 7~12%, Ni-P
Coating performance is excellent.
Buffer
Due to there is H in nickel process+It generates, gradually decreases solution ph with plating process, in order to stablize plating
Speed and guarantee quality of coating, chemical nickel plating system must be maintained within the scope of certain pH value.
As an implementation, the buffer includes but is not limited to borax, sodium acetate, acetic acid, succinic acid, succinic acid
Hydrogen sodium, natrium hydrocitricum, malonic acid hydrogen sodium, boric acid.
As a preferred embodiment, the buffer is sodium acetate and acetic acid, the sodium acetate and acetic acid it is dense
Degree is than being 1:1.
The application offsets external a little acid or alkali and dilution by the way that sodium acetate, acetic acid and other components interaction is added
Influence to solution ph variation, is allowed to fluctuate in a smaller range.
Stabilizer
Chemical nickel-plating solution is a thermodynamic unstable system, for various reasons, if hot-spot, pH value are excessively high,
Or inevitably there are some active particles in the plating solution in certain impurity effects, make plating solution that fierce self-catalyzed reaction occur
A large amount of Ni-P black powders are generated, plating solution is caused to be decomposed in a short time, escape a large amount of bubbles, cause the economic damage that can not be saved
It loses.The application inhibits the Auto-decomposition of plating solution by the way that stabilizer is added, and carries out plating process orderly under control.
The stabilizer is selected from compound, the oxygenatedchemicals, heavy metal ion, water solubility of group vi element S, Se, Te
At least one of organic matter.
The example of compound as group vi element S, Se, Te, including but not limited to thiocarbamide, modified thiocarbamide, thio sulphur
Hydrochlorate, rhodanate.
As the example of oxygenatedchemicals, including but not limited to AsO2 -、IO3 -、BrO3 -、MoO4 2-。
As the example of heavy metal ion, including but not limited to Pb2+、Sn2+、Sb3+。
As the example of water soluble organic substance, including but not limited to maleic acid, itaconic acid.
As a preferred embodiment, the stabilizer is isothiourea propane sulfonic acid inner salt, the isothiourea propane sulfonic acid
Inner salt purchase reaches Science and Technology Co., Ltd. in the excellent generation in Hubei.
When the concentration of reducing agent is 30~40g/L in chemical nickel-plating liquid, be conducive to form complete coating in matrix surface；But
It is that increasing for reducing agent will lead to the stability of plating solution and reduce, by the way that the stabilizer is added, improves the stability of plating solution.This
Stabilizer described in application can inhibit H2PO2 -Reduction, the stabilizer preferential oxidation, the stabilizer ejected electron after oxidation makes
Ni2+It is reduced to Ni, the stabilizer in the state of oxidation is restored by hypophosphites.Applicants have discovered that the stabilizer and other
Component mutually cooperates with, and while realizing bath stability, the speed of separating out of nickel can still maintain 6-9 μ inch/min (84 DEG C).
Complexing agent
As a preferred embodiment, the complexing agent includes glacial acetic acid, hydroxyacetic acid, lactic acid, oxalic acid, the third two
Acid, succinic acid, tartaric acid, glycine, alanine, salicylic acid, ethylenediamine tetra-acetic acid, malic acid, citric acid, aspartic acid, third
At least one of acid.
As a preferred embodiment, the complexing agent includes oxalic acid, citric acid, propionic acid.
Preferably, the concentration ratio of the oxalic acid, citric acid, propionic acid are as follows: 1:1:(4~10).
It is highly preferred that the concentration ratio of the oxalic acid, citric acid, propionic acid are as follows: 1:1:5.
Oxalic acid is called ethanedioic acid, colourless monocline sheet or prism crystallization or white powder, ion group in aqueous solution
It is divided into: C2O4 2-(oxalate denominationby), H+(hydrogen ion), HC2O4 -(oxalic acid hydrogen radical ion).
Citric acid also known as citric acid, No. CAS is 77-92-9, and the citric acid is a kind of tricarboxylic acid compounds, a kind of
Stronger organic acid has 3 H+It can ionize；Heating can resolve into multi-products, react with acid, alkali, glycerol etc..Institute
State the dissociation constant of citric acid are as follows: pK1=3.13；PK2=4.76；PK3=6.40, in the pH value condition of chemical nickel plating operation
Under, most of citric acid has all been ionized into the citrate ion of trivalent.
Propionic acid, No. CAS is 79-09-4, short chain saturated fatty acid, colourless oil liquid.The propionic acid can be bought, can also
With self-control.The propionic acid can be obtained by lower carbon number hydrocarbons direct oxidation method, i.e., energy when producing acetic acid as feed oxygen metaplasia using lower carbon number hydrocarbons
Propionic acid can be obtained after separation in formate and propionic acid；The propionic acid can also be obtained by Lei Pofa, i.e., ethylene is in carbonyl nickel
One-step synthesis propionic acid is reacted with carbon monoxide and water under catalytic action.Reaction condition is 250~320 DEG C and 10~30MPa.
As a preferred embodiment, the complexing agent further includes lactic acid.
The oxalic acid, citric acid, lactic acid, propionate concentration ratio are as follows: 1:1:(1~4): 5.
Preferably, the oxalic acid, citric acid, lactic acid, propionate concentration ratio are as follows: 1:1:2:5.
Applicants have discovered that after complexing agent is adsorbed on matrix surface, improving the work of reaction after the complexing agent is added
Property, discharging active atomic hydrogen for hypophosphorous acid root provides more activation energies, to improve nickel layer speed of separating out, especially works as institute
Complexing agent is stated as oxalic acid, citric acid, lactic acid, propionic acid, and the oxalic acid, citric acid, lactic acid, propionate concentration ratio are as follows: 1:1:(1~
4): when 5, can reduce the porosity of plated film, conjecture is because one side oxalic acid, citric acid, lactic acid, propionic acid and nickel ion are formed
The complex compound of various structures, the stability difference of different complexes, while the complexing agent system form intermolecular with sodium hypophosphite
Hydrogen bond promotes H2PO2-Oxidation, so as to control orderly precipitating nickel, another party's complexing agent system is adsorbed on substrate table
Face makes the nickle atom being precipitated in the intermolecular progress ordering growth of the complexing agent of absorption and bunched, to reduce the hole of plated film
Rate.
Auxiliary agent
As an implementation, the auxiliary agent includes succinate sodium salt, neopelex, dodecyl sulphur
At least one of sour sodium.
As a preferred embodiment, the auxiliary agent is lauryl sodium sulfate.
Since the valence link power of atom on the surface of solids or molecule is unsaturated, with inside atom on solid-liquid interface
Or molecule compares that energy is relatively high, especially metal surface is the column for belonging to high energy surface.By the way that dodecane is added in the application
Base sodium sulphate makes the solid-air interface of chemical plating system be easy to be replaced by solid-liquid interface.
The preparation method of the chemical nickel-plating liquid, is not particularly limited.
As an implementation, the preparation method of the chemical nickel-plating liquid, comprising the following steps:
(1) deionized water that prewired plating solution volume fraction is 50% is added at room temperature；
(2) then complexing agent, nickel salt, buffer is sequentially added under agitation to stir to whole dissolutions,
(3) remaining ionized water is added, reducing agent, stabilizer, auxiliary agent is added and stirs to whole dissolutions；Again with sulfuric acid tune
Save pH value be 4.1-5.0 to get.
The mixing speed is 500-1500rpm.
The third aspect of the present invention provides a kind of nickel plating product, by impregnating workpiece to be plated in the nickel-plating liquid with shape
It is prepared at the mode of plated film.
The workpiece to be plated includes but is not limited to: PCB circuit board, aluminium oxide ceramic substrate, aluminum nitride ceramic substrate, metal
Substrate.
The nickel coating the preparation method comprises the following steps: chemical nickel-plating liquid is heated to 80-90 degrees Celsius, by being put into of workpiece to be plated
Plating 10-40min in nickel-plating liquid is learned, that is, is prepared.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment
Embodiment 1
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 12g/L, nickel salt 18g/L,
Reducing agent 30g/L, buffer 1g/L, stabilizer 8ppm, auxiliary agent 80ppm.
The complexing agent be oxalic acid, citric acid, propionic acid, the oxalic acid, citric acid, propionic acid concentration ratio are as follows: 1:1:4；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, comprising the following steps:
(1) deionized water that prewired plating solution volume fraction is 50% is added at room temperature；
(2) then complexing agent, nickel salt, buffer is sequentially added under agitation to stir to whole dissolutions,
(3) remaining ionized water is added, reducing agent, stabilizer, auxiliary agent is added and stirs to whole dissolutions；Again with sulfuric acid tune
Save pH value be 4.5 to get.
The mixing speed is 800rpm.
Embodiment 2
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 30g/L, nickel salt 30g/L,
Reducing agent 40g/L, buffer 4g/L, stabilizer 18ppm, auxiliary agent 120ppm.
The complexing agent be oxalic acid, citric acid, propionic acid, the oxalic acid, citric acid, propionic acid concentration ratio are as follows: 1:1:4；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 3
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, propionic acid, the oxalic acid, citric acid, propionic acid concentration ratio are as follows: 1:1:4；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 4
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, propionic acid, the oxalic acid, citric acid, propionic acid concentration ratio are as follows: 1:1:10；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 5
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, propionic acid, the oxalic acid, citric acid, propionic acid concentration ratio are as follows: 1:1:5；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 6
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, lactic acid, propionic acid, the oxalic acid, citric acid, lactic acid, propionic acid concentration ratio
Are as follows: 1:1:1:5；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 7
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, lactic acid, propionic acid, the oxalic acid, citric acid, lactic acid, propionic acid concentration ratio
Are as follows: 1:1:4:5；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 8
A kind of high stability chemical nickel-plating liquid, the component comprising following levels: complexing agent 18g/L, nickel salt 20g/L,
Reducing agent 35g/L, buffer 2g/L, stabilizer 12ppm, auxiliary agent 108ppm.
The complexing agent be oxalic acid, citric acid, lactic acid, propionic acid, the oxalic acid, citric acid, lactic acid, propionic acid concentration ratio
Are as follows: 1:1:2:5；
The nickel salt is nickel acetate；
The reducing agent is sodium hypophosphite；
The buffer is sodium acetate and acetic acid, and the concentration ratio of the sodium acetate and acetic acid is 1:1.
The stabilizer is isothiourea propane sulfonic acid inner salt, and the isothiourea propane sulfonic acid inner salt purchase reaches science and technology in the excellent generation in Hubei
Limited liability company.
The auxiliary agent is lauryl sodium sulfate.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 9
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 8, the difference lies in that the stabilizer is
Thiocarbamide.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 10
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 5, the difference lies in that the oxalic acid, lemon
The concentration ratio of acid, propionic acid are as follows: 1:1:1.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 11
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 5, the difference lies in that the oxalic acid, lemon
The concentration ratio of acid, propionic acid are as follows: 1:1:15.
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 12
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 8, the difference lies in that the oxalic acid, lemon
Acid, lactic acid, propionic acid concentration ratio are as follows: 1:1:0.5:5；
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 13
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 8, the difference lies in that the oxalic acid, lemon
Acid, lactic acid, propionic acid concentration ratio are as follows: 1:1:6:5；
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Embodiment 14
A kind of high anti-corrosion chemical nickel-plating liquid, concrete component and concentration are with embodiment 8, the difference lies in that the oxalic acid, lemon
Acid, malonic acid, propionic acid concentration ratio are as follows: 1:1:2:5；
The preparation method of the chemical nickel-plating liquid, the specific steps are the same as those in embodiment 1.
Performance test
The chemical nickel-plating liquid that embodiment 1-14 is provided carries out nickel plating, method are as follows: by chemical nickel-plating liquid to printed circuit board
84 degrees Celsius are heated to, printed circuit board is put into plating 20min in chemical nickel-plating liquid, that is, is prepared.To each embodiment system
Standby product carries out porosity test, the results are shown in Table 1.
(1) porosity test:
Test method are as follows: under conditions of 23 ± 3 degrees Celsius of temperature, relative humidity < 55%, nitric acid is poured into beaker,
It is placed in drier, covers lid, place 30 ± 5min；Sample to be tested polytetrafluoroethylene (PTFE) adhesive tape is bound, is hung on dry
In dry device；Sample takes out after placing 75 ± 5min, in 15 degree of incandescent lamp oblique angle parallel radiation, and observes under 1000 power microscopes
The hole number being corroded.
Hole number judgment criteria is as follows:
| Pore-size | Calculate hole number |
| Maximum gauge≤0.05mm | 0 |
| 0.05mm < maximum gauge < 0.1mm | 1 |
| 0.1mm≤maximum gauge < 0.2mm | 2 |
| Maximum gauge >=0.2mm | 5 |
Judgment criteria: every square millimeter≤5 are qualified product, are otherwise rejected product.
(2) bath stability is tested: carrying out stability test, test method are as follows: take 100mL to the nickel-plating liquid of each embodiment
Chemical nickel-plating liquid is heated to 84 degrees Celsius, and 1mL palladium chloride activating solution is instilled into chemical nickel-plating liquid, and (concentration is the chlorine of 100mg/L
Change aqueous palladium), the time of plating solution decomposition is observed and recorded, the results are shown in Table 1.
1. the performance test results of table
Examples 1 to 8 the nickel speed of separating out of nickel-plating liquid be 6-9 μ inch/min (84 DEG C), the nickel of embodiment 10 is precipitated
Speed is 3 μ inch/min (84 DEG C).
The above is only presently preferred embodiments of the present invention, is not the limitation for making other forms to invention, any
Those skilled in the art are changed or are changed to the equivalent of equivalent variations possibly also with the technology contents of the disclosure above
Embodiment, but without departing from the technical solutions of the present invention, above embodiments are made according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of high stability chemical nickel-plating liquid, which is characterized in that the component comprising following levels: 12~30g/ of complexing agent
L, 18~30g/L of nickel salt, 30~40g/L of reducing agent, 1~4g/L of buffer, 8~18ppm of stabilizer,
Wherein, the complexing agent includes oxalic acid, citric acid, propionic acid.
2. chemical nickel-plating liquid as described in claim 1, which is characterized in that the reducing agent include sodium hypophosphite, sodium borohydride,
At least one of alkyl amine borine, hydrazine.
3. chemical nickel-plating liquid as claimed in claim 2, which is characterized in that the reducing agent is sodium hypophosphite.
4. chemical nickel-plating liquid as described in claim 1, which is characterized in that the nickel salt includes nickel sulfate, nickel chloride, acetic acid
At least one of nickel, nickel sulfamic acid, nickelous hypophosphite.
5. chemical nickel-plating liquid as claimed in claim 4, which is characterized in that the nickel salt is nickel acetate.
6. chemical nickel-plating liquid as described in claim 1, which is characterized in that further include the component of following levels: auxiliary agent 80
~120ppm.
7. chemical nickel-plating liquid as claimed in claim 6, which is characterized in that the auxiliary agent includes succinate sodium salt, dodecane
At least one of base benzene sulfonic acid sodium salt, lauryl sodium sulfate.
8. chemical nickel-plating liquid as claimed in claims 6 or 7, which is characterized in that the auxiliary agent is lauryl sodium sulfate.
9. a kind of preparation method of such as described in any item chemical nickel-plating liquids of claim 6~8, which is characterized in that including following
Step:
(1) deionized water that prewired plating solution volume fraction is 50% is added at room temperature；
(2) then complexing agent, nickel salt, buffer is sequentially added under agitation to stir to whole dissolutions,
(3) remaining ionized water is added, reducing agent, stabilizer, auxiliary agent is added and stirs to whole dissolutions；Sulphur acid for adjusting pH is used again
Value be 4.1-5.0 to get.
10. a kind of nickel plating product, which is characterized in that by impregnating workpiece to be plated in nickel plating according to any one of claims 1 to 8
Liquid is prepared in a manner of forming plated film.
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