Summary of the invention
It is an object of the invention to solve at least the above problems, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of neodymium iron boron nickel plating solution and preparation method thereof, application method and electricityPlating piece can satisfy the requirement of the combination force request, salt spray test of the neodymium iron boron product of different size, shape, plating piece performanceIt is good.
In order to realize these purposes and other advantages according to the present invention, a kind of neodymium iron boron nickel plating solution is provided, is wrappedInclude the component of following concentration: the nickel sulfate of 250-300g/L, the magnesium sulfate of 15-25g/L, the sodium sulphate of 40-50g/L, 10-15g/The sodium chloride of L, the boric acid of 40-60g/L, the acetic acid of 1-3g/L, the saccharin of 0.5-0.8g/L, the sodium fluoride of 3-5g/L, surplus areWater.
Preferably, further include the component of following concentration: 0.05g/L is to ethylbenzene sulfonamide, the 3- butine -1- of 0.1g/LAlcohol, 0.04g/L sodium toluene sulfinate, 0.4g/L Sodium Allyl Sulfonate.
The preparation method of neodymium iron boron nickel plating solution, including following preparation step:
S1, add position at pure water to electroplating bath 2/3, be warming up to 60-70 DEG C；
S2, the component that concentrations above is added, stirring make it completely dissolved；
S3, nickelous carbonate is added, adjusts pH value to 4.8-5.2；
S4,2-4mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
S5,2-4g/L active carbon is added, stirs 2h, stand 6-8h；
S6, filtering；
S7, pH value is adjusted to 4.0-4.8 with 10wt.% sulfuric acid；
It S8, with corrugated sheet by current density is 0.1-0.4A/dm2It is electrolysed 6h or more, until low current density area is by black dullUntil becoming light gray.
Preferably, further include following maintenance step:
A, chemical examination is primary weekly, carries out supplement each component to concentrations above according to result of laboratory test；
B, 1-2mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
C, active carbon filters 4h；
It D, is 0.1-0.4A/dm by current density with corrugated sheet2It is electrolysed 4h or more, until low current density area is by black dull changeUntil light gray.
Neodymium iron boron plated item is electroplated in neodymium iron boron nickel plating solution by neodymium iron boron product and is obtained.
Preferably, the neodymium iron boron plated item is the neodymium iron boron plated item that surface has nickel coating.
The application method of neodymium iron boron nickel plating solution adjusts the pH value of neodymium iron boron nickel plating solution to 4.0-5.5, is heated up to40-60 DEG C, the neodymium iron boron product through oil removing and pickling is immersed in neodymium iron boron magnetic body nickel plating solution as cathode, with metallic nickelAs anode, it is passed through direct current, obtains coating.
Preferably, molten to neodymium iron boron magnetic body electronickelling before neodymium iron boron product being immersed neodymium iron boron magnetic body nickel plating solutionLiquid is passed through inert gas to 3MPa, and stirring, pressure maintaining 1h, then pressure release to atmospheric pressure, is cooled to room temperature, is evacuated to negative pressure.
The present invention is include at least the following beneficial effects:
The first, invention increases the magnesium sulfate of 15-25g/L, 40-50g/L sodium sulphate as conductive salt, enhance moltenThe conductive capability of liquid, improves current density, improves current efficiency, also shortens the time of nickel coating, improves productThe binding force of matrix and coating, can also have to the pin hole generated in electroplating process it is certain make up effect, magnesium ion and sodium fromFor son in the plating solution there are certain Surface flat, plating crystallization is fine and smooth, and there also have to the salt spray test for extending big product to be certain goodPlace substitutes nickel chloride with sodium chloride, can reduce certain electroplating cost；
The second, increase in formula of the invention to ethylbenzene sulfonamide, 3- butyne-1-ol, sodium toluene sulfinate, allylSodium sulfonate is adsorbed on the growing point of cathode by unsaturated carbon bond, is increased cathodic polarization, is tended to the cathode surface speed of growthUnanimously, adsorption and desorption dynamic equilibrium balances coating tensile stress, reduces the crystallite dimension of coating, keep coating ductility good, pin holeIt is few, high pressure dissolution-vacuum separation of inert gas is carried out, plating solution raw materials are flattened, the exoelectrical reaction of nickel ion when hindering to be electroplated,The growth for inhibiting coating cleaning makes the crystal grain deposited on cathode is well-regulated to be parallel to matrix surface arrangement, crystal grain refinement, coatingIt is bright.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by thisThe research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
Below with reference to example, the present invention is described in further detail, to enable those skilled in the art referring to specification textWord can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or moreThe presence or addition of a other elements or combinations thereof.
It should be noted that experimental method described in following embodiments is unless otherwise specified conventional method, instituteReagent and material are stated, unless otherwise specified, is commercially obtained.
<example 1>
Neodymium iron boron nickel plating solution, the component including following concentration: the nickel sulfate of 250g/L, the magnesium sulfate of 15g/L, 40g/The sodium sulphate of L, the sodium chloride of 10g/L, the boric acid of 40g/L, the acetic acid of 1g/L, the saccharin of 0.5g/L, the sodium fluoride of 3g/L, surplusFor water.
Preparation method the following steps are included:
S1, add position at pure water to electroplating bath 2/3, be warming up to 60-70 DEG C；
S2, the component that concentrations above is added, stirring make it completely dissolved；
S3, nickelous carbonate is added, adjusts pH value to 4.8-5.2；
S4,2mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
S5,2g/L active carbon is added, stirs 2h, stand 6h；
S6, filtering；
S7, pH value is adjusted to 4.0-4.8 with 10wt.% sulfuric acid；
It S8, with corrugated sheet by current density is 0.1A/dm2It is electrolysed 6h or more, until low current density area is become from black dullUntil light gray.
The application method of neodymium iron boron nickel plating solution adjusts the pH value of neodymium iron boron nickel plating solution to 4.0-5.5, is heated up to40 DEG C, the neodymium iron boron product through oil removing and pickling is immersed in neodymium iron boron magnetic body nickel plating solution as cathode, is made with metallic nickelFor anode, it is passed through direct current, obtains coating.
<example 2>
Neodymium iron boron nickel plating solution, the component including following concentration: the nickel sulfate of 300g/L, the magnesium sulfate of 25g/L, 50g/The sodium sulphate of L, the sodium chloride of 15g/L, the boric acid of 60g/L, the acetic acid of 3g/L, the saccharin of 0.8g/L, the sodium fluoride of 5g/L, surplusFor water.
Preparation method the following steps are included:
S1, add position at pure water to electroplating bath 2/3, be warming up to 60-70 DEG C；
S2, the component that concentrations above is added, stirring make it completely dissolved；
S3, nickelous carbonate is added, adjusts pH value to 4.8-5.2；
S4,4mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
S5,4g/L active carbon is added, stirs 2h, stand 8h；
S6, filtering；
S7, pH value is adjusted to 4.0-4.8 with 10wt.% sulfuric acid；
It S8, with corrugated sheet by current density is 0.4A/dm2It is electrolysed 6h or more, until low current density area is become from black dullUntil light gray.
The application method of neodymium iron boron nickel plating solution adjusts the pH value of neodymium iron boron nickel plating solution to 4.0-5.5, is heated up to60 DEG C, the neodymium iron boron product through oil removing and pickling is immersed in neodymium iron boron magnetic body nickel plating solution as cathode, is made with metallic nickelFor anode, it is passed through direct current, obtains coating.
<example 3>
Neodymium iron boron nickel plating solution, the component including following concentration: the nickel sulfate of 280g/L, the magnesium sulfate of 20g/L, 45g/The sodium sulphate of L, the sodium chloride of 12g/L, the boric acid of 50g/L, the acetic acid of 3g/L, the saccharin of 0.6g/L, the sodium fluoride of 4g/L, surplusFor water.
Preparation method the following steps are included:
S1, add position at pure water to electroplating bath 2/3, be warming up to 60-70 DEG C；
S2, the component that concentrations above is added, stirring make it completely dissolved；
S3, nickelous carbonate is added, adjusts pH value to 4.8-5.2；
S4,3mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
S5,3g/L active carbon is added, stirs 2h, stand 7h；
S6, filtering；
S7, pH value is adjusted to 4.0-4.8 with 10wt.% sulfuric acid；
It S8, with corrugated sheet by current density is 0.3A/dm2It is electrolysed 6h or more, until low current density area is become from black dullUntil light gray.
The application method of neodymium iron boron nickel plating solution adjusts the pH value of neodymium iron boron nickel plating solution to 4.0-5.5, is heated up to50 DEG C, the neodymium iron boron product through oil removing and pickling is immersed in neodymium iron boron magnetic body nickel plating solution as cathode, is made with metallic nickelFor anode, it is passed through direct current, obtains coating.
<example 4>
Neodymium iron boron nickel plating solution, the component including following concentration: the nickel sulfate of 280g/L, the magnesium sulfate of 20g/L, 45g/The sodium sulphate of L, the sodium chloride of 12g/L, the boric acid of 50g/L, the acetic acid of 3g/L, the saccharin of 0.6g/L, the sodium fluoride of 4g/L,0.05g/L is to ethylbenzene sulfonamide, the 3- butyne-1-ol of 0.1g/L, 0.04g/L sodium toluene sulfinate, 0.4g/L allyl sulphurSour sodium, surplus are water.
Preparation method the following steps are included:
S1, add position at pure water to electroplating bath 2/3, be warming up to 60-70 DEG C；
S2, the component that concentrations above is added, stirring make it completely dissolved；
S3, nickelous carbonate is added, adjusts pH value to 4.8-5.2；
S4,3mL/L hydrogen peroxide is added, 2h is inflated in stirring, and hydrogen peroxide is added in the form of the hydrogen peroxide solution of 10vol.%；
S5,3g/L active carbon is added, stirs 2h, stand 7h；
S6, filtering；
S7, pH value is adjusted to 4.0-4.8 with 10wt.% sulfuric acid；
It S8, with corrugated sheet by current density is 0.3A/dm2It is electrolysed 6h or more, until low current density area is become from black dullUntil light gray.
The application method of neodymium iron boron nickel plating solution adjusts the pH value of neodymium iron boron nickel plating solution to 4.0-5.5, is heated up to50 DEG C, inert gas is passed through to 3MPa, stirring, pressure maintaining 1h, then pressure release to atmospheric pressure, drop to neodymium iron boron magnetic body nickel plating solutionIt warms to room temperature, is evacuated to negative pressure, be heated up to 50 DEG C, it is molten that the neodymium iron boron product through oil removing and pickling is immersed neodymium iron boron magnetic body electronickellingIt is used as cathode in liquid, using metallic nickel as anode, is passed through direct current, obtains coating.
<comparative example 1>
Neodymium iron boron nickel plating solution is formulated with example 3, unlike, the content of magnesium sulfate is 4g/L.
Preparation method is the same as example 3.
<comparative example 2>
Neodymium iron boron nickel plating solution is formulated with example 3, unlike, the content of magnesium sulfate is 35g/L.
Preparation method is the same as example 3.
<comparative example 3>
Neodymium iron boron nickel plating solution is formulated with example 3, unlike, not containing magnesium sulfate and sodium sulphate, and general in formulaThe sodium chloride of 12g/L is substituted for the nickel chloride of 45g/L.
Preparation method is the same as example 3.
<thickness of coating Consistency test>
Neodymium iron boron nickel plating solution prepared by example 3, comparative example 1, comparative example 2 carries out nickel plating, same plated item intoRow analysis of experiments, as shown in Figure 1, 2, test result is as shown in table 1, it can be seen that 3 high current area of example and low current area differenceRange is 1.8-2.3, average value 1.97, fluctuation range 0.5；1 high current area of comparative example and low current area difference range are2.1-3.2, average value 2.84, fluctuation range 0.9；2 high current area of comparative example and low current area difference range are 2.8-3.6,Average value is 3.12, fluctuation range 0.8；To sum up, 3 high current area of example and low current area difference are minimum, and fluctuation is minimum.
Table 1
<binding force and salt spray test>
Neodymium iron boron nickel plating solution prepared by example 3, comparative example 3 carries out nickel plating, and same plated item carries out test pointAnalysis, test result is as shown in table 2, it can be seen that in combining power test, in 10 tests of comparative example 3, have 2 times it is unqualified, noQualification rate is 80%, and 10 tests of example 3 have 0 unqualified, disqualification rate 0%, are better than comparative example 3；Salt spray testIn, in 10 times of comparative example 3 tests, salt spray test duration is between 36-48h, in 10 tests of example 3, when salt spray testIt grows between 96-114h, 2.5 times of salt spray test duration increase or more is with the obvious advantage.Same plated item, with galvanization coating thicknessSubject to 15 μm of degree, between 2.9-3.7, average value is 3.27 μm, and real for the high current area of comparative example 3 and the difference in low current area3 high current area of example and low current area difference are between 1.8-2.3, average value 1.97, and the consistency of thickness of coating is better than comparative example3。
Table 2
<plating performance test>
Neodymium iron boron nickel plating solution prepared by example 3, example 4, comparative example 3 carries out nickel plating, and same plated item carries outAnalysis of experiments (current density 4A/dm2), test result is as shown in table 3, it can be seen that the formula of example 4 is significant better than example 3Better than comparative example 3.
Classification reference standard of the detection of coating bright property according to the bright sex experience rating method of range estimation being commonly used,The classification reference standard are as follows:
1 grade: bright in mirror surface: coating is as bright as a sixpence, can clearly differentiate the face and eyebrow of people；
2 grades: bright: coating surface is bright, it is seen that people's face and eyebrow, but eyebrow part is not clear enough；
3 grades: half is bright: coating surface light is poor, but can find out the face profile of people, eyebrow obscure portions；
4 grades: without light: coating is substantially matt, does not see the facial face profile of people；
The detection of plating solution deposition velocity:
It is weighed respectively with electronic balance with sample weight after plating before plating, it is fast using the weight gain of unit time endobasal-body as depositionDegree,
Deposition velocity=(sample weight before sample weight-nickel plating after nickel plating)/electroplating time
The detection of plating solution current efficiency:
Current efficiency refers generally to cathode efficiency, the ratio of theory consumption electricity and actual consumption electricity, actual consumptionElectricity is calculated by the electrochemical equivalent of size of current, time, deposited metal,
Current efficiency=(sample weight before sample weight-nickel plating after nickel plating)/(electric current × electroplating time used when platingThe electrochemical equivalent of × cathode deposition) × 100%
The detection of solution dispersibility:
The measurement of dispersibility is using far and near cathode method, and far and near cathode ratio at a distance from anode is 2:1, and beaker both ends are respectively hungOne size is 20mm × 30mm, is used as cathode with a thickness of the copper sheet of 0.5mm, one and cathode size are hung between two cathodesEqual automatically controlled or netted nickel sheet as anode,
Dispersibility=(far and near cathode is at a distance from anode than weight gain/remote cathode weight gain of-nearly cathode)/(far and near yinPole is at a distance from anode than weight gain/remote cathode weight gain -2 of+nearly cathode) × 100%
Table 3
| Bright property | Deposition velocity (mg/h) | Current efficiency (%) | Dispersibility (%) |
| Example 3 | 2 | 267 | 94.12 | 40.11 |
| Example 4 | 1 | 289 | 95.66 | 47.75 |
| Comparative example 3 | 3 | 169.5 | 89.57 | 21.58 |
Number of devices and treatment scale described herein are for simplifying explanation of the invention.To application of the invention,Modifications and variations will be readily apparent to persons skilled in the art.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listedWith it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easilyRealize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimitedIn specific details and example shown and described herein.