CN113881997B - Preparation method of nickel-cobalt-based nano composite coating for sintering neodymium iron boron - Google Patents
Preparation method of nickel-cobalt-based nano composite coating for sintering neodymium iron boron Download PDFInfo
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- CN113881997B CN113881997B CN202111449896.8A CN202111449896A CN113881997B CN 113881997 B CN113881997 B CN 113881997B CN 202111449896 A CN202111449896 A CN 202111449896A CN 113881997 B CN113881997 B CN 113881997B
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The invention belongs to the technical field of rare earth permanent magnet material surface electroplating corrosion prevention, and provides a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron, which comprises the following steps: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated; preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution, and mixing the nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain proportion to obtain a composite nickel-cobalt base nano electroplating solution; electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min; the composite nickel-cobalt-based nano electroplating solution provided by the invention has the advantages of simple preparation method, stable process conditions, low pollution and capability of industrial production, and the nickel-cobalt-based nano composite plating layer has good binding force with the sintered neodymium-iron-boron substrate, is bright and compact and further improves the corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of rare earth permanent magnet material surface electroplating corrosion prevention, and relates to a preparation method of a nickel-cobalt-based nano composite coating for sintered neodymium iron boron.
Background
The rare earth neodymium iron boron permanent magnetic material is used as a third-generation rare earth permanent magnetic material, has light weight, small volume, extremely high magnetic energy and coercive force, and can be widely applied to various motors. Because the interior of the neodymium iron boron permanent magnet material is of a multi-phase structure, once a neodymium-rich phase is corroded, the neodymium iron boron main phase crystal grains can fall off, and pulverization is caused. Therefore, the application and development of the rare earth neodymium iron boron permanent magnet material can not be separated from the innovation and promotion of the anticorrosion technology.
As in application No.: CN201410263544.7 discloses a neodymium iron boron magnet nickel electroplating method, which specifically comprises a pretreatment process, a nickel pre-plating process, a water washing process, a semigloss nickel plating process, a water washing process, a bright nickel plating process and a water washing process for a neodymium iron boron magnet, wherein a first nickel electroplating solution composed of nickel sulfate, boric acid, sodium succinate salt, sodium carboxyethyl sulfonate and water is adopted in the nickel pre-plating process, a second nickel electroplating solution composed of nickel sulfate, diammonium hydrogen citrate, boric acid, ammonia water and water is adopted in the semigloss nickel plating process, chloride ions are not contained in the first nickel electroplating solution, the sodium succinate salt and sodium carboxyethyl sulfonate are contained in the first nickel electroplating solution, and a proper amount of diammonium hydrogen citrate is contained in the second nickel electroplating solution.
As in application No.: CN201210282935.4 discloses a neodymium iron boron magnet nickel electroplating solution and a use method thereof, aiming at overcoming the defects of uneven thickness distribution and higher porosity of the prior neodymium iron boron magnet nickel electroplating layer, the formula of the neodymium iron boron magnet nickel electroplating solution is as follows: 80-350g/L of nickel sulfate, 20-80g/L of nickel chloride, 30-55g/L of boric acid, 0.1-5g/L of yttrium sulfate, 0.04-2g/L of nano silicon dioxide and the balance of water.
At present, the plating layers for electroplating protection and industrial application on the surface of neodymium iron boron mainly comprise Ni, Ni-Cu-Ni and the like. The surface of a common plating layer of electroplated single-layer Ni has more pores and poor corrosion resistance, the preparation process of the electroplated Ni-Cu-Ni is complex and the cost is high, and the chemical plating of Ni can cause serious pollution to the environment, so that how to prepare a plating layer which has high compactness, thin plating layer thickness, low stress and large binding force between the plating layer and a substrate becomes a problem to be solved urgently in the field of rare earth neodymium iron boron corrosion prevention at present.
Disclosure of Invention
The invention provides a preparation method of a nickel-cobalt-based nano composite coating for sintered neodymium-iron-boron, aiming at solving the problems of high compactness, thin coating thickness, low stress and large binding force between the coating and a substrate.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated;
s2: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s3: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s4: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s5: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron, and forming a nickel-cobalt-based nano composite coating on the surface of the sintered neodymium iron boron;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100-120 ℃, and fully stirring to maintain the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: one or more Al2O3、SiO2、ZrO2Nanoparticles, one or more graphene, MoS2Adding into absolute ethyl alcoholUltrasonic cleaning is carried out;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain a composite nano material additive solution;
preferably, the composite nano material additive solution is prepared at the moment of use so as to ensure the dispersibility of the composite nano material additive solution.
Preferably, the nickel-cobalt alloy electroplating solution contains 250 g/L-320 g/L of nickel sulfate; the content of nickel chloride is 50 g/L-100 g/L; the content of the cobalt sulfate is 40 g/L-60 g/L; the boric acid content is 50 g/L-80 g/L; the content of sodium sulfate is 10 g/L-30 g/L; the content of magnesium sulfate is 10 g/L-50 g/L; the content of the sodium dodecyl sulfate is 0.1 g/L-0.8 g/L.
Preferably, Al in the composite nanomaterial additive solution2O3Nanoparticles, SiO2Nanoparticles and ZrO2The particle size distribution range of the nano particles is between 50nm and 500nm, the micro morphology is similar to spherical, wherein, Al2O3Nanoparticles, SiO2Nanoparticles and ZrO2The total content of the nano particles is 10 g/L-20 g/L; graphene and MoS2One or more of the total content of the components is 0.1 g/L-10 g/L; the total content of one or more of polyethylene glycol and tertiary butanol is 0.2 g/L-1.0 g/L; the content of ammonium sulfate is 1.0 g/L-3.0 g/L.
Preferably, the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is controlled to be 8: 1-5: 1.
Preferably, the pH value of the nickel-cobalt alloy electroplating solution is 4.5-6.0, and the temperature is 35-45 ℃.
Preferably, the stirring speed is 200 r/min-300 r/min in the process of preparing the nickel-cobalt alloy electroplating solution.
Preferably, the nickel-cobalt-based nanocomposite coating may be used for an intermediate layer of a single-layer anticorrosive coating or a multi-layer anticorrosive coating.
Preferably, the pre-treatment comprises the steps of:
s1: grinding and chamfering the sintered neodymium iron boron for 2-12 h according to the actual condition of the sintered neodymium iron boron product;
s2: performing sand blasting treatment on the sintered neodymium iron boron subjected to chamfering grinding by using a sand blasting machine;
s3: removing grease on the surface of the sintered neodymium iron boron by using an alkaline degreasing agent;
s4: using HNO3Carrying out ultrasonic cleaning on rust and an oxide layer on the surface by using the solution;
s5: using H2SO4Or activating the surface of the sintered neodymium iron boron by using an ammonium bifluoride solution;
preferably, the abrasive used in the sand blasting process is one or more of zirconia, alumina and silica, and the particle size of the abrasive is in the range of 0.3 mm-0.6 mm.
The invention has the beneficial effects that:
1. compared with the traditional plating solution, the composite nickel-cobalt-based nano plating solution disclosed by the invention is simple to prepare, nano material particles can be uniformly dispersed in the composite nickel-cobalt-based nano plating solution, the phenomenon of large-scale agglomeration cannot be formed, the plating process is stable, and the composite nickel-cobalt-based nano plating solution can be better applied to industrial production.
2. Compared with the traditional nickel plating layer, the nickel-cobalt-based nano composite plating layer prepared by the invention has low internal stress and high compactness, effectively reduces the content of nickel in the plating layer, and has better high-reduction characteristic while ensuring excellent anti-corrosion performance.
3. The nickel-cobalt-based nano composite coating prepared by the invention is bright and compact, and through using the composite nano material additive solution, the nano materials in the composite nano material additive solution are uniformly distributed on the surface of the coating, so that the porosity of the coating is reduced, the coating has good binding force with the sintered neodymium iron boron base material, and the corrosion resistance of the sintered neodymium iron boron can be obviously improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the present invention for preparing a nickel-cobalt-based nanocomposite coating;
FIG. 2 is a surface topography diagram of a plating layer without adding dispersant ammonium sulfate and tert-butyl alcohol;
FIG. 3 is a surface topography diagram of a plating layer with dispersant ammonium sulfate and tert-butyl alcohol added according to the present invention;
FIG. 4 shows that the three-dimensional nanomaterial Al is added on the basis of the original graphene additive2O3And (3) a plating surface topography of the nanoparticles.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Comparative example one, described in conjunction with fig. 2:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s2: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s3: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s4: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100 ℃, fully stirring, and maintaining the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy plating solution;
the preparation method of the composite nano material additive solution comprises the steps of adding 12g/L of graphene into absolute ethyl alcohol for ultrasonic cleaning;
wherein, in the nickel-cobalt alloy electroplating solution, 270g/L of nickel sulfate; 60g/L of nickel chloride; 50g/L of cobalt sulfate; boric acid 70 g/L; 10g/L of sodium sulfate; magnesium sulfate 25 g/L; sodium dodecyl sulfate 0.3 g/L.
Wherein the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is controlled to be 7: 1.
The pH value of the composite nickel-cobalt-based nano electroplating solution is 4.5-6.0, and the temperature is 35-45 ℃.
In the process of preparing the nickel-cobalt alloy electroplating solution, the stirring speed is 240 r/min.
Comparative example two, described with reference to fig. 2 and 3:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s2: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s3: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s4: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100 ℃, fully stirring, and maintaining the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: mixing one or more of graphene and MoS2Adding the mixture into absolute ethyl alcohol for ultrasonic cleaning;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain an additive solution;
the composite nano material additive solution needs to be prepared in use so as to ensure the dispersibility of the composite nano material additive solution.
Wherein, in the nickel-cobalt alloy electroplating solution, 270g/L of nickel sulfate; 60g/L of nickel chloride; 50g/L of cobalt sulfate; boric acid 70 g/L; 10g/L of sodium sulfate; magnesium sulfate 25 g/L; sodium dodecyl sulfate 0.3 g/L.
Wherein the content of graphene is 12 g/L; the content of tertiary butanol is 0.3 g/L; the content of ammonium sulfate was 1.5 g/L.
Wherein the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is 7: 1.
The pH value of the composite nickel-cobalt-based nano electroplating solution is 4.5-6.0, and the temperature is 35-45 ℃.
The stirring speed is 240 r/min.
Comparative example three, described with reference to fig. 3 and 4:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s2: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s3: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s4: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100 ℃, fully stirring, and maintaining the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: one or more Al2O3、SiO2、ZrO2Nanoparticles, one or more graphene, MoS2Adding the mixture into absolute ethyl alcohol for ultrasonic cleaning;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain an additive solution;
the additive solution is prepared at present when in use so as to ensure the dispersibility of the additive solution.
Wherein, in the nickel-cobalt alloy electroplating solution, the concentration of nickel sulfate is 310 g/L; 85g/L of nickel chloride; 55g/L of cobalt sulfate; 50g/L of boric acid; 25g/L of sodium sulfate; magnesium sulfate 40 g/L; sodium dodecyl sulfate 0.7 g/L.
Wherein, the graphene is 10 g/L; al (Al)2O34g/L of nanoparticles; polyethylene glycol 0.3 g/L.
Wherein the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is 5: 1.
The pH value of the composite nickel-cobalt-based nano electroplating solution is 4.5-6.0, and the temperature is 35-45 ℃.
The stirring speed is 240 r/min.
Embodiment one, combine fig. 1:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated;
s2: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s3: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s4: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s5: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100 ℃, fully stirring, and maintaining the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy plating solution;
the preparation method of the composite nano material additive solution comprises the steps of adding 12g/L of graphene into absolute ethyl alcohol for ultrasonic cleaning;
wherein, in the nickel-cobalt alloy electroplating solution, 270g/L of nickel sulfate; 60g/L of nickel chloride; 50g/L of cobalt sulfate; boric acid 70 g/L; 10g/L of sodium sulfate; magnesium sulfate 25 g/L; sodium dodecyl sulfate 0.3 g/L.
Wherein the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is controlled to be 7: 1.
The pH value of the composite nickel-cobalt-based nano electroplating solution is 5.5, and the temperature is 35-45 ℃.
The stirring speed is 240 r/min.
The pretreatment comprises the following steps:
and chamfering the sintered neodymium iron boron for 3 hours by using a vibrating mill, and controlling the angle of the workpiece to be about 0.35.
And (4) sand blasting for 15min to enable the surface of the sintered neodymium iron boron to have certain roughness.
Degreasing the chamfer sand-blasted workpiece for 40min to remove surface oil stains, wherein the degreasing agent is an alkaline degreasing agent and mainly comprises sodium carbonate, sodium silicate and an emulsifier, the temperature of the degreasing agent is 50 ℃, and the degreasing time is 20 min.
The washing time after oil removal is 2 min.
And (3) carrying out acid cleaning and rust removal twice by using dilute nitric acid with the mass fraction of 7%, wherein the acid cleaning time is 90 s.
And carrying out three-stage countercurrent washing after acid washing, wherein the washing time is 2 min.
Activating with activating solution for 60s, and washing with water for 2 min.
The temperature is controlled to be about 45 ℃ in the electroplating process, and the cathode current density is 0.7A/dm2The magnetic stirring speed is 220r/min, and the electroplating time is 70 min.
And (4) washing the electroplated sintered neodymium iron boron product for 2min, washing for 15s by using a surfactant solution, and drying and storing.
Example two:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated;
s2: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s3: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s4: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s5: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100 ℃, fully stirring, and maintaining the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: one or more Al2O3、SiO2、ZrO2Nanoparticles, one or more graphene, MoS2Adding the mixture into absolute ethyl alcohol for ultrasonic cleaning;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain an additive solution;
the composite nano material additive solution needs to be prepared at present when in use so as to ensure the dispersibility of the additive solution.
Wherein, in the nickel-cobalt alloy electroplating solution, the concentration of nickel sulfate is 310 g/L; 85g/L of nickel chloride; 55g/L of cobalt sulfate; 50g/L of boric acid; 25g/L of sodium sulfate; magnesium sulfate 40 g/L; sodium dodecyl sulfate 0.7 g/L.
Wherein, the graphene is 10 g/L; al (Al)2O34g/L of nanoparticles; polyethylene glycol 0.3 g/L.
Wherein the volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is controlled to be 5: 1.
The PH value of the nickel-cobalt-based nano composite plating solution is 4.5-6.0, and the temperature of the plating solution is 35-45 ℃.
The stirring speed is 240 r/min.
The pretreatment comprises the following steps:
and chamfering the sintered neodymium iron boron for 3 hours by using a vibrating mill, and controlling the angle of the workpiece to be about 0.35.
And (4) sand blasting for 15min to enable the surface of the sintered neodymium iron boron to have certain roughness.
Degreasing the chamfer sand-blasted workpiece for 40min to remove surface oil stains, wherein the degreasing agent is an alkaline degreasing agent and mainly comprises sodium carbonate, sodium silicate and an emulsifier, the temperature of the degreasing agent is 50 ℃, and the degreasing time is 20 min.
The washing time after oil removal is 2 min.
And (3) carrying out acid cleaning and rust removal twice by using dilute nitric acid with the mass fraction of 7%, wherein the acid cleaning time is 90 s.
And carrying out three-stage countercurrent washing after acid washing, wherein the washing time is 2 min.
Activating with activating solution for 60s, and washing with water for 2 min.
The temperature is controlled to be about 45 ℃ in the electroplating process, and the cathode current density is 0.7A/dm2The magnetic stirring speed is 220r/min, and the electroplating time is 70 min.
And (4) washing the electroplated sintered neodymium iron boron product for 2min, washing for 15s by using a surfactant solution, and drying and storing.
The working principle of the invention is as follows:
a preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron comprises the following steps:
s1: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated;
s2: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s3: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s4: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s5: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron to form a nickel-cobalt-based nano composite coating;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100-120 ℃, and fully stirring to maintain the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: one or more Al2O3、SiO2、ZrO2Nanoparticles, one or more graphene, MoS2Adding the mixture into absolute ethyl alcohol for ultrasonic cleaning;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain a composite nano material additive solution;
the composite nano material additive solution needs to be prepared in use so as to ensure the dispersibility of the composite nano material additive solution.
The nickel-cobalt alloy electroplating solution contains 250 g/L-320 g/L of nickel sulfate; the content of nickel chloride is 50 g/L-100 g/L; the content of the cobalt sulfate is 40 g/L-60 g/L; the boric acid content is 50 g/L-80 g/L; the content of sodium sulfate is 10 g/L-30 g/L; the content of magnesium sulfate is 10 g/L-50 g/L; the content of the sodium dodecyl sulfate is 0.1 g/L-0.8 g/L.
Al in the composite nano material additive solution2O3Nanoparticles, SiO2Nanoparticles and ZrO2The particle size distribution range of the nano particles is between 50nm and 500nm, the micro morphology is similar to spherical, wherein, Al2O3Nanoparticles, SiO2Nanoparticles and ZrO2The total content of the nano particles is 10 g/L-20 g/L; graphene, MoS2One or more of the total content is 0.1 g/L-10 g/L; the total content of one or more of polyethylene glycol and tertiary butanol is 0.2 g/L-1.0 g/L; the content of ammonium sulfate is 1.0 g/L-3.0 g/L.
The volume ratio of the nickel-cobalt alloy electroplating solution to the composite nano material additive solution is controlled to be 8: 1-5: 1.
The pH value of the composite nickel-cobalt-based nano electroplating solution is 4.5-6.0, and the temperature is 35-45 ℃.
The stirring speed is 200 r/min-300 r/min.
The nickel-cobalt-based nano composite coating can be used as a single-layer anticorrosive coating or a middle layer of a multi-layer anticorrosive coating.
The pretreatment comprises the following steps:
s1: grinding and chamfering the sintered neodymium iron boron for 2-12 h according to the actual condition of the sintered neodymium iron boron product;
s2: performing sand blasting treatment on the sintered neodymium iron boron subjected to chamfering grinding by using a sand blasting machine;
s3: removing grease on the surface of the sintered neodymium iron boron by using an alkaline degreasing agent;
s4: using HNO3Carrying out ultrasonic cleaning on rust and an oxide layer on the surface by using the solution;
s5: using H2SO4Or activating the surface of the sintered neodymium iron boron by using an ammonium bifluoride solution;
the abrasive used in the sand blasting process is one or more of zirconia, alumina and silicon dioxide, and the grain diameter of the abrasive is within the range of 0.3 mm-0.6 mm.
By performing a microstructure test on the surface of the sintered neodymium iron boron according to the first comparative example and the second comparative example, compared with a nickel-cobalt-based composite plating solution without adding ammonium sulfate and tert-butyl alcohol as dispersants, the nano-particle material graphene in the second comparative example is uniformly dispersed in the plating solution without large-scale agglomeration, and as shown in fig. 2 and 3, the nano-particle material can be uniformly deposited in an alloy plating layer due to the addition of the dispersant, so that the electroplating process is stable; the microstructure test of the surface of the sintered neodymium iron boron is carried out through the second comparative example and the third comparative example, and the three-dimensional nano material Al is added on the basis of the original graphene additive2O3The nano particles are shown in fig. 4, compared with two-dimensional nano material graphene, the nano particles can be better embedded in the metal alloy coating, so that the porosity of the coating is lower, as shown in fig. 4, the corrosion resistance of the coating is obviously improved, the third comparative example is compared with the first and second examples, and the density and the wettability of the nickel-cobalt-based nano composite coating can be obviously improved by performing pretreatment before electroplating on the sintered neodymium-iron-boron.
The technical specifications of the coatings obtained by the above examples are shown in the following table
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof; the present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any minor modifications, equivalent replacements and improvements made to the above embodiment according to the technical spirit of the present invention should be included in the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a nickel-cobalt-based nano composite coating for sintering neodymium iron boron is characterized by comprising the following steps:
s1: before electroplating the sintered neodymium iron boron, the surface of the sintered neodymium iron boron needs to be pretreated;
s2: preparing a nickel-cobalt alloy electroplating solution and a composite nano material additive solution;
s3: mixing the prepared nickel-cobalt alloy electroplating solution and the composite nano material additive solution according to a certain volume ratio to form a composite nickel-cobalt base nano electroplating solution;
s4: electroplating the surface of the sintered neodymium iron boron by using the composite nickel cobalt base nano electroplating solution, wherein the electroplating time is controlled to be 60-120 min;
s5: carrying out deionized water cleaning, surface conditioning and drying treatment on the electroplated sintered neodymium iron boron, and forming a nickel-cobalt-based nano composite coating on the surface of the sintered neodymium iron boron;
the preparation method of the nickel-cobalt alloy electroplating solution comprises the following steps:
s1: dissolving nickel sulfate, nickel chloride and cobalt sulfate in deionized water, heating to 100-120 ℃, and fully stirring to maintain the main salt solution at 35-45 ℃;
s2: respectively adding boric acid, sodium sulfate, magnesium sulfate and lauryl sodium sulfate into deionized water, fully dissolving, adding into a main salt solution, and fully stirring to obtain a nickel-cobalt alloy electroplating solution;
the preparation method of the composite nano material additive solution comprises the following steps:
s1: one or more Al2O3、SiO2、ZrO2Nanoparticles, one or more graphene, MoS2Adding the mixture into absolute ethyl alcohol for ultrasonic cleaning;
s2: dissolving one or more of ammonium sulfate, polyethylene glycol and tert-butyl alcohol in deionized water to prepare a dispersion liquid;
s3: adding the cleaned nano material into the dispersion liquid, and carrying out ultrasonic treatment and stirring for 2 hours to obtain a composite nano material additive solution;
the pretreatment comprises the following steps:
s1: grinding and chamfering the sintered neodymium iron boron for 2-12 h according to the actual condition of the sintered neodymium iron boron product;
s2: performing sand blasting treatment on the sintered neodymium iron boron subjected to chamfering grinding by using a sand blasting machine;
s3: removing grease on the surface of the sintered neodymium iron boron by using an alkaline degreasing agent;
s4: using HNO3Carrying out ultrasonic cleaning on rust and an oxide layer on the surface by using the solution;
s5: using H2SO4Or activating the surface of the sintered neodymium iron boron by using an ammonium bifluoride solution;
the abrasive used in the sand blasting process is one or more of zirconia, alumina and silicon dioxide, and the grain diameter of the abrasive is within the range of 0.3 mm-0.6 mm.
2. The method as claimed in claim 1, wherein the composite nanomaterial additive solution is prepared to ensure dispersibility of the composite nanomaterial additive solution.
3. The method for preparing the nickel-cobalt-based nano composite coating of sintered neodymium-iron-boron according to claim 1, wherein the nickel-cobalt alloy electroplating solution contains 250g/L to 320g/L of nickel sulfate; the content of nickel chloride is 50 g/L-100 g/L; the content of the cobalt sulfate is 40 g/L-60 g/L; the boric acid content is 50 g/L-80 g/L; the content of sodium sulfate is 10 g/L-30 g/L; the content of magnesium sulfate is 10 g/L-50 g/L; the content of the sodium dodecyl sulfate is 0.1 g/L-0.8 g/L.
4. The method as claimed in claim 1, wherein the Al in the solution of the nano-composite additive is Al2O3Nanoparticles, SiO2Nanoparticles and ZrO2The particle size distribution range of the nano particles is between 50nm and 500nm, the micro morphology is similar to spherical, wherein, Al2O3Nanoparticles, SiO2Nanoparticles and ZrO2The total content of the nano particles is 10 g/L-20 g/L; graphene and MoS2One or more of the total content of the components is 0.1 g/L-10 g/L; the total content of one or more of polyethylene glycol and tertiary butanol is 0.2 g/L-1.0 g/L; the content of ammonium sulfate is 1.0 g/L-3.0 g/L.
5. The method as claimed in claim 1, wherein the ratio of the volume of the nickel-cobalt alloy electroplating solution to the volume of the composite nanomaterial additive solution is controlled to be 8: 1-5: 1.
6. The method as claimed in claim 1, wherein the ni-co based nanocomposite coating for sintered nd-fe-b has a PH of 4.5-6.0 and a temperature of 35-45 ℃.
7. The method as claimed in claim 1, wherein the stirring speed is 200 r/min-300 r/min during the preparation of the ni-co alloy electroplating solution.
8. The method for preparing the nickel-cobalt-based nano composite coating for sintered neodymium-iron-boron according to claim 1, wherein the nickel-cobalt-based nano composite coating can be used as a single-layer anticorrosive coating or an intermediate layer of a multi-layer anticorrosive coating.
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