CN105420703A - Ultrasonic chemical nickel and phosphorus plating method for NdFeB material - Google Patents
Ultrasonic chemical nickel and phosphorus plating method for NdFeB material Download PDFInfo
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- CN105420703A CN105420703A CN201510957609.2A CN201510957609A CN105420703A CN 105420703 A CN105420703 A CN 105420703A CN 201510957609 A CN201510957609 A CN 201510957609A CN 105420703 A CN105420703 A CN 105420703A
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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
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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
- C23C18/1601—Process or apparatus
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
Abstract
The invention belongs to the technical field of a chemical plating process and particularly relates to an ultrasonic chemical nickel and phosphorus plating method for an NdFeB material. The method comprises the following steps: mechanical grinding; ultrasonic degreasing; acid pickling and rust removing; flash plating; ultrasonic chemical nickel and phosphorus plating. Compared with a general chemical plating method, the ultrasonic chemical nickel and phosphorus plating method for the NdFeB material, disclosed by the invention, has the advantages that the plating temperature is low, a plated layer is more compact, better corrosion resistance is realized and the plated layer has a better binding force with a base body.
Description
Technical field
The invention belongs to chemical plating technology technical field, particularly a kind of Electroless Nickel plating with Ultrasonic phosphorus method for NdFeB material.
Background technology
NdFeB rare earth permanent-magnetic material, compared with common material, has very high magnetic energy product, coercive force and remanent magnetism, just because of having so excellent performance, makes it have the advantage do not replaced in a lot of fields.But because the chemically reactive of rare earth permanent-magnetic material itself is stronger, corrosion resisting property is poor, therefore must carry out effective surface treatment to it, make it not only will have high electromagnetic performance, high physical strength, also will have high corrosion resistance nature.
Chemical plating nickel-phosphorus alloy is fine and close with coating structure, thickness distribution is even, hardness is high, erosion resistance is strong, profiling is good, affect the advantage such as little to magnetic property becomes the etch-proof ideal chose of rare earth permanent-magnetic material.
But traditional chemical plating technology is difficult at rare-earth permanent magnet coating surface, this is because NdFeB rare earth permanent-magnetic material is normally by the method compression moulding of powder metallurgy and final sintering and/or bonding, magnet surface is coarse, loose porous, be easy to remain corrosive solution in hole, corrosive solution etch hole inwall gradually residual after causing electroless plating; After after a while, make matrix and coating bonding surface place corrode efflorescence gradually, coating entirety comes off.Therefore effective pre-treating technology will be taked to reach sealing of hole and to improve the object of matrix and the long-term bonding strength of coating.Different pre-treating technologies, to quality of coating, particularly has a significant impact binding force of cladding material, covering power.And the uniform fold of coating and be improve the corrosion proof key factor of NdFeB overlay coating with combining closely of matrix.
At present, the energy input form of conventional chemical nickel phosphorus plating technique is mainly heating in water bath, and acidic chemical is plated in more than 85 DEG C to carry out, and alkali electroless is plated in 70 ~ 75 DEG C to carry out, and energy consumption is large, and easily deposits on cell wall.In plating process, moisture evaporation is fast, and plating solution is easily aging, poor stability, and reductive agent ortho phosphorous acid sodium utilization is low; Meanwhile, high temperature also can cause the modification of some plated material, thus limits its application to a certain extent.
Ultrasonic wave, as a kind of new energy input form, can improve the sedimentation velocity of nickel-phosphorus alloy in chemical nickel phosphorus plating technique significantly, reduces the phosphorus content in nickel-phosphorus alloy, improves the microhardness of coating, reduces the porosity of coating significantly; Under ul-trasonic irradiation, the sedimentation velocity of nickel-phosphorus alloy is about without 1.5 during ultrasonic wave times, reaches as high as 10 μm/more than h.Study the metallographic structure of sonochemistry coating, composition, stuctures and properties, and compare with conventional chemical coating, result of study shows that sonochemistry coating microstructure is fine and close, cell structure refinement, deposit in acidic electroless Ni electrolyte reduces, and is mainly non-crystalline state, accompanies a small amount of crystallite.
Summary of the invention
The object of the present invention is to provide a kind of Electroless Nickel plating with Ultrasonic phosphorus method for NdFeB permanent magnet material, the method carries out sealing of hole and activation by the mode of flash in alkali plating solution to NdFeB permanent magnet material, and carries out chemical nickel phosphorus plating by ultrasonic assistant mode.
For achieving the above object, technical scheme of the present invention is as follows:
For an Electroless Nickel plating with Ultrasonic phosphorus method for NdFeB permanent magnet material, comprise the steps:
A) mechanical grinding: NdFeB sample is polished, clean with distilled water flushing;
B) ultrasonic oil removing: adopt ultrasonic wave mode to the NdFeB sample oil removing after mechanical grinding in degreasing fluid, the oil removing time is 10 ~ 15min, and clean with distilled water flushing;
C) acid pickling and rust removing: in acid pickling and rust removing liquid, acid pickling and rust removing is carried out to the NdFeB sample after ultrasonic oil removing, the acid pickling and rust removing time is 30 ~ 40s, and clean with distilled water flushing;
D) flash: the NdFeB sample after acid pickling and rust removing is immersed in alkali plating solution and carries out flash, and clean with distilled water flushing, wherein, consisting of of alkali plating solution: NiSO
46H
2o25 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 60 ~ 68ml/L, thiocarbamide 0.0018 ~ 0.0022g/L, surplus is distilled water, plating solution pH>=12, and the flash time is 3 ~ 5min;
E) Electroless Nickel plating with Ultrasonic phosphorus: the NdFeB sample after flash is immersed in nickel plating phosphorus solution and carries out Electroless Nickel plating with Ultrasonic phosphorus, wherein, consisting of of described nickel plating phosphorus solution: NiSO
47H
2o26 ~ 30g/L, NaH
2pO
224 ~ 27g/L, Na
3c
6h
5o
72H
2o28 ~ 31g/L, CH
3cOONa18 ~ 22g/L, succsinic acid 1.0 ~ 1.2g/L, lead acetate 0.0001 ~ 0.0002g/L, surplus is distilled water, these nickel plating phosphorus solution pH=8 ~ 8.5, and nickel plating phosphorus solution temperature controls at 63 ~ 65 DEG C, and plating time is 40 ~ 45min.
Step a) in, NdFeB sample plane and edge are polished successively.
Step b) in, consisting of of described degreasing fluid: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Step c) in, consisting of of described acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Steps d) in, regulate alkali plating solution pH value with NaOH, make plating solution pH >=12.
Step e) in, regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8 ~ 8.5.
Beneficial effect of the present invention is:
First by flash, for there is surface irregularity and having the NdFeB permanent magnet material of higher porosity, mainly play the effect of sealing of hole, thus avoid sample directly to immerse in chemical plating fluid, serious corrosion and dissolving occur; By ultrasonic assistant chemical nickel phosphorus plating, provide a kind of new energy input, chemical nickel phosphorus plating technique is carried out with higher plating speed when reducing bath temperature, make coating even compact more by hyperacoustic cavatition, improve the bonding force of coating and matrix and the corrosion resistance nature etc. of coating simultaneously.Compared with plating with conventional chemical, the Electroless Nickel plating with Ultrasonic phosphorus technique plating temperature for NdFeB permanent magnet material of the present invention is low, plated layer compact, anti-corrosion capability and better with the bonding force of matrix.
Accompanying drawing explanation
Fig. 1 a is the coating morphology that embodiment 3 adopts conventional chemical Ni-P-plating technique and obtains under 75 DEG C of conditions;
Fig. 1 b is the coating morphology that embodiment 4 adopts Electroless Nickel plating with Ultrasonic phosphorus technique of the present invention and obtains under 65 DEG C of conditions;
Fig. 2 a is that embodiment 3 adopts conventional chemical Ni-P-plating technique under 75 DEG C of conditions, obtain the cross-section morphology of coating;
Fig. 2 b is that embodiment 4 adopts Electroless Nickel plating with Ultrasonic phosphorus technique of the present invention under 65 DEG C of conditions, obtain the cross-section morphology of coating;
Fig. 3 is the dynamic potential polarization curve of embodiment 3 conventional chemical coating and embodiment 4 sonochemistry coating.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.
By carrying out pH resistance test to NdFeB permanent magnet material, found that NdFeB permanent magnet material is in the acidic solution that pH value is low, along with the reduction of pH value, weightless increase and material corrosion speed are accelerated, when pH value is greater than 7, the corrosion speed of sample obviously declines, and during pH=11.23, sample weightlessness is zero.When pH value rises to about 14, sample weightlessness is still zero, therefore, herein by use strong alkali solution, flash is carried out to NdFeB permanent magnet material and carry out sealing of hole, thin film is formed at NdFeB specimen surface, then carry out chemical nickel phosphorus plating on this basis, thus the coating making to obtain light is level and smooth, coating microstructure even uniform.
Electroless Nickel plating with Ultrasonic phosphorus method for NdFeB permanent magnet material of the present invention, comprises the steps:
A) mechanical grinding: polish to NdFeB sample, polishes successively to NdFeB sample plane and edge, makes NdFeB specimen surface evenly bright, and clean with distilled water flushing;
B) ultrasonic oil removing: adopt ultrasonic wave mode to the NdFeB sample oil removing after mechanical grinding in degreasing fluid, the oil removing time is 10 ~ 15min, and clean with distilled water flushing, wherein, consisting of of described degreasing fluid: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water;
C) acid pickling and rust removing: in acid pickling and rust removing liquid, acid pickling and rust removing is carried out to the NdFeB sample after ultrasonic oil removing, the acid pickling and rust removing time is 30 ~ 40s, and clean with distilled water flushing, wherein, consisting of of described acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water;
D) flash: the NdFeB sample after acid pickling and rust removing is immersed in alkali plating solution and carries out flash, and clean with distilled water flushing, wherein, consisting of of alkali plating solution: NiSO
46H
2o25 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 60 ~ 68ml/L, thiocarbamide 0.0018 ~ 0.0022g/L, surplus is distilled water, and regulate alkali plating solution pH value with NaOH, make basic solution pH>=12, the flash time is 3 ~ 5min;
E) Electroless Nickel plating with Ultrasonic phosphorus: the NdFeB sample after flash is immersed Electroless Nickel plating with Ultrasonic phosphorus in nickel plating phosphorus solution, wherein, consisting of of described nickel plating phosphorus solution: NiSO
47H
2o26 ~ 30g/L, NaH
2pO
224 ~ 27g/L, Na
3c
6h
5o
72H
2o28 ~ 31g/L, CH
3cOONa18 ~ 22g/L, succsinic acid 1.0 ~ 1.2g/L, lead acetate 0.0001 ~ 0.0002g/L, surplus is distilled water, regulates nickel plating phosphorus solution pH value, make nickel plating phosphorus solution pH=8 ~ 8.5 with ammoniacal liquor, nickel plating phosphorus solution temperature controls at 63 ~ 65 DEG C, and plating time is 40 ~ 45min.
The present invention is by selecting the alkali plating solution of pH >=12; at room temperature flash is carried out to NdFeB sample; NdFeB specimen surface is made to form catalytic membrane; thus protection matrix and play the effect of activation; and then carry out Electroless Nickel plating with Ultrasonic phosphorus, obtain even compact and with matrix in conjunction with good nickel-phosphorus coating.When reducing plating temperature, introduce in electroless plating ultrasonic energy effectively improve electroless plating sedimentation rate and obtain coating microstructure particle more tiny, arrangement tightr, plated layer compact imporosity, improves bonding force and the corrosion resistance nature of chemical plating simultaneously.
Embodiment 1 (prior art)
The NdFeB sample that embodiment 1 adopts is bonding NdFeB sample, and specification is Φ 24mm*3mm thin rounded flakes, and the chemical nickel phosphorus plating technique of embodiment 1 is as follows:
Mechanical grinding → ultrasonic oil removing 10min → acid pickling and rust removing 30s → activation 30s → conventional chemical nickel plating phosphorus.
Wherein, the consisting of of degreasing fluid in ultrasonic oil removing: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Consisting of of acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Activating recipe is sulphosalicylic acid 20g/L, ammonium bifluoride 10g/L, and surplus is distilled water.
The consisting of of nickel plating phosphorus solution in conventional chemical nickel plating phosphorus: NiSO
47H
2o28g/L, NaH
2pO
224g/L, Na
3c
6h
5o
72H
2o28g/L, CH
3cOONa18g/L, succsinic acid 1.0g/L, lead acetate 0.0001g/L, surplus is distilled water, and regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8, nickel plating phosphorus solution temperature controls at 75 DEG C, and plating time is 60min.
Embodiment 2 (prior art)
The NdFeB sample that embodiment 2 adopts is bonding NdFeB sample, and specification is Φ 24mm*3mm thin rounded flakes, and the chemical nickel phosphorus plating technique of embodiment 2 is as follows:
Mechanical grinding → physics sealing of hole → ultrasonic oil removing 10min → acid pickling and rust removing 30s → activation 30s → conventional chemical nickel plating phosphorus.
Wherein, the consisting of of degreasing fluid in ultrasonic oil removing: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Consisting of of acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Physics sealing of hole adopts Zinic stearas, Zinic stearas is heated to 160 DEG C, makes it be molten state, then put into by the sample through cleaning, take out after impregnating by pressure 20min, now specimen surface and hole all cover by the Zinic stearas that solidifies voluntarily.
Activating recipe is sulphosalicylic acid 20g/L, ammonium bifluoride 10g/L, and surplus is distilled water.
The consisting of of nickel plating phosphorus solution in conventional chemical nickel plating phosphorus: NiSO
47H
2o30g/L, NaH
2pO
225g/L, Na
3c
6h
5o
72H
2o31g/L, CH
3cOONa22g/L, succsinic acid 1.3g/L, lead acetate 0.0002g/L, surplus is distilled water, and regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8.5, nickel plating phosphorus solution temperature controls at 75 DEG C, and plating time is 60min.
Embodiment 3 (prior art)
The NdFeB sample that embodiment 3 adopts is bonding NdFeB sample, and specification is Φ 24mm*3mm thin rounded flakes, and the chemical nickel phosphorus plating technique of embodiment 3 is as follows:
Mechanical grinding → ultrasonic oil removing 10min → acid pickling and rust removing 30s → flash 3min → conventional chemical nickel plating phosphorus.
Wherein, the consisting of of degreasing fluid in ultrasonic oil removing: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Consisting of of acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Consisting of of alkali plating solution in flash: NiSO
46H
2o25g/L, HEDP60ml/L, thiocarbamide 0.0018g/L, surplus is distilled water, and regulate basic solution pH value with NaOH, make basic solution pH=12, the flash time is 3min.
The consisting of of nickel plating phosphorus solution in conventional chemical nickel plating phosphorus: NiSO
47H
2o28g/L, NaH
2pO
224g/L, Na
3c
6h
5o
72H
2o28g/L, CH
3cOONa18g/L, succsinic acid 1.0g/L, lead acetate 0.0001g/L, surplus is distilled water, and regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8.2, nickel plating phosphorus solution temperature controls at 75 DEG C, and plating time is 60min.
Embodiment 4 (the present invention)
The NdFeB sample that embodiment 4 adopts is bonding NdFeB sample, and specification is Φ 24mm*3mm thin rounded flakes, and the chemical nickel phosphorus plating technique of embodiment 4 is as follows:
Mechanical grinding → ultrasonic oil removing 10min → acid pickling and rust removing 30s → flash 3min → Electroless Nickel plating with Ultrasonic phosphorus 45min.
Wherein, the consisting of of degreasing fluid in ultrasonic oil removing: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Consisting of of acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Consisting of of alkali plating solution in flash: NiSO
46H
2o25g/L, HEDP60ml/L, thiocarbamide 0.0018g/L, surplus is distilled water, regulates basic solution pH value, make basic solution pH=12 with NaOH.
The consisting of of nickel plating phosphorus solution in Electroless Nickel plating with Ultrasonic phosphorus: NiSO
47H
2o26g/L, NaH
2pO
224g/L, Na
3c
6h
5o
72H
2o28g/L, CH
3cOONa18g/L, succsinic acid 1.0g/L, lead acetate 0.0001g/L, surplus is distilled water, and regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8, nickel plating phosphorus solution temperature controls at 65 DEG C.
Embodiment 5 (the present invention)
The NdFeB sample that embodiment 5 adopts is bonding NdFeB sample, and specification is Φ 24mm*3mm thin rounded flakes, and the chemical nickel phosphorus plating technique of embodiment 5 is as follows:
Mechanical grinding → ultrasonic oil removing 15min → acid pickling and rust removing 40s → flash 5min → Electroless Nickel plating with Ultrasonic phosphorus 40min.
Wherein, the consisting of of degreasing fluid in ultrasonic oil removing: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
Consisting of of acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
Consisting of of alkali plating solution in flash: NiSO
46H
2o30g/L, HEDP68ml/L, thiocarbamide 0.0022g/L, surplus is distilled water, regulates basic solution pH value, make basic solution pH=13 with NaOH.
The consisting of of nickel plating phosphorus solution in Electroless Nickel plating with Ultrasonic phosphorus: NiSO
47H
2o30g/L, NaH
2pO
227g/L, Na
3c
6h
5o
72H
2o31g/L, CH
3cOONa22g/L, succsinic acid 1.2g/L, lead acetate 0.0002g/L, surplus is distilled water, and regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8.5, nickel plating phosphorus solution temperature controls at 63 DEG C.
The comparison of the coating sedimentation rate of the chemical nickel phosphorus plating of the NdFeB permanent magnet material of embodiment 1 ~ 5, porosity and surface topography, as shown in table 1.
The comparison of table 1 embodiment 1 ~ 5 quality of coating
Electroless plating is carried out to after NdFeB sample pretreating by the pre-treatment of embodiment 1, chemical plating fluid decomposes, its reason is that embodiment 1 does not carry out sealing of hole, NdFeB permanent magnetic material surface has hole, if do not carry out sealing of hole, the mordant aqueous solution of lower tape is easy in hole, to cause in plating process raffinate etch hole inwall and there is Ni-P reduction deposition in plating process while gradually, the dissolving of NdFeB can be carried out simultaneously, due to the existence of hole, the boron ash that neodymium iron boron inside is oozed out enters chemical plating fluid, thus have impact on the stability of plating solution, plating solution is caused to decompose.
Embodiment 2 adopts Zinic stearas to carry out physics sealing of hole then to adopt weakly acidic solution to activate, embodiment 2 coating surface is coarse has stain and uneven coating is even, find in process of the test, although have employed Zinic stearas to carry out physics sealing of hole to sample, but when pickling time is more than 15s, specimen surface becomes ash immediately, specimen surface is oxidized, this shows that hole sealing agent is washed in the long meeting of pickling time off, destroy sealing of hole effect, and the follow-up acid pickling and rust removing carried out of sample after sealing of hole all carries out under acid state with activation.If but soak time is inadequate, sample plating is more difficult, and follow-up bath temperature is higher, and therefore hole sealing agent is in molten state, and volatility is larger.Therefore, although the sample outline after sealing of hole is better than the sample of non-sealing of hole, but surface still has mushy existence perhaps, thus at the position, corner of the sample blind spot having plating leakage all in various degree, and corrosion produces in plating leakage place substantially, corrosive medium gos deep into matrix gradually then, matrix and coating junction is corroded gradually efflorescence, therefore eliminate blind spot, make coating uniform fold be improve one of corrosion proof key.
Embodiment 3 ~ 5 be in alkali plating solution sample being placed on pH >=12 flash 3 ~ 5min to replace sealing of hole in embodiment 1,2 and activating process, after taking out, visual inspection can see that specimen surface covers thin film, after plating, edge is without plating leakage phenomenon, essentially eliminate blind spot, improve covering power, coating light, level and smooth, coating microstructure even uniform.
Simultaneously, comparing embodiment 3 and embodiment 4,5, can find out, embodiment 4,5 electroless plating reaction speed is apparently higher than embodiment 3, and sedimentation rate is faster, and porosity is less, this is because, in electroless plating, introduce ultrasonic energy effectively improve the sedimentation rate of electroless plating and the coating microstructure particle obtained is more tiny, arrangement is more tight, plated layer compact imporosity.
Fig. 1 a is the coating morphology that embodiment 3 adopts conventional chemical Ni-P-plating technique and obtains under 75 DEG C of conditions; Fig. 1 b is the coating morphology that embodiment 4 adopts Electroless Nickel plating with Ultrasonic phosphorus technique of the present invention and obtains under 65 DEG C of conditions; Comparison diagram 1a and 1b can find out, compared with conventional coating, the tissue particles of sonochemistry coating is more tiny, arrangement is more tight, can intactly cover whole matrix thus the hole of minimizing coating surface.
Fig. 2 a is that embodiment 3 adopts conventional chemical Ni-P-plating technique under 75 DEG C of conditions, obtain the cross-section morphology of coating; Fig. 2 b is that embodiment 4 adopts Electroless Nickel plating with Ultrasonic phosphorus technique of the present invention under 65 DEG C of conditions, obtain the cross-section morphology of coating; Comparison diagram 2a and 2b can find out, compared with conventional coating, sonochemistry coating is evenly densification, and coating is combined tightr with matrix, middle without obvious separation surface and groove, and bonding force is better.
Fig. 3 is the dynamic potential polarization curve of embodiment 3 conventional chemical coating and embodiment 4 sonochemistry coating, as can be seen from Figure 3 ultrasonic coating is compared with conventional coating, the positive 100mv of corrosion potential, corrosion electric current density reduces 6 ~ 7 times, and the dynamic potential polarization curve of ultrasonic coating has obviously passive area, this coating obtained under ultrasonic field is described has better thermodynamic stability and electrochemistry corrosion resistance nature.
Indicate the coating even compact formed by ultrasonic assistant chemical nickel phosphorus plating in sum, good with the bonding force of matrix, corrosion resistance nature improves greatly.
Claims (6)
1., for an Electroless Nickel plating with Ultrasonic phosphorus method for NdFeB permanent magnet material, it is characterized in that:
Comprise the steps:
A) mechanical grinding: NdFeB sample is polished, clean with distilled water flushing;
B) ultrasonic oil removing: adopt ultrasonic wave mode to the NdFeB sample oil removing after mechanical grinding in degreasing fluid, the oil removing time is 10 ~ 15min, clean with distilled water flushing;
C) acid pickling and rust removing: in acid pickling and rust removing liquid, acid pickling and rust removing is carried out to the NdFeB sample after ultrasonic oil removing, the acid pickling and rust removing time is 30 ~ 40s, clean with distilled water flushing;
D) flash: the NdFeB sample after acid pickling and rust removing is immersed in alkali plating solution and carries out flash, and with distilled water flushing, wherein, consisting of of alkali plating solution: NiSO
46H
2o25 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 60 ~ 68ml/L, thiocarbamide 0.0018 ~ 0.0022g/L, surplus is distilled water, plating solution pH>=12, and the flash time is 3 ~ 5min;
E) Electroless Nickel plating with Ultrasonic phosphorus: the NdFeB sample after flash is immersed in nickel plating phosphorus solution and carries out Electroless Nickel plating with Ultrasonic phosphorus, wherein, consisting of of described nickel plating phosphorus solution: NiSO
47H
2o26 ~ 30g/L, NaH
2pO
224 ~ 27g/L, Na
3c
6h
5o
72H
2o28 ~ 31g/L, CH
3cOONa18 ~ 22g/L, succsinic acid 1.0 ~ 1.2g/L, lead acetate 0.0001 ~ 0.0002g/L, surplus is distilled water, these nickel plating phosphorus solution pH=8 ~ 8.5, and nickel plating phosphorus solution temperature controls at 63 ~ 65 DEG C, and plating time is 40 ~ 45min.
2., as claimed in claim 1 for the Electroless Nickel plating with Ultrasonic phosphorus method of NdFeB permanent magnet material, it is characterized in that:
Step a) in, NdFeB sample plane and edge are polished successively.
3., as claimed in claim 1 for the Electroless Nickel plating with Ultrasonic phosphorus method of NdFeB permanent magnet material, it is characterized in that:
Step b) in, consisting of of described degreasing fluid: NaOH10g/L, Na
3pO
470g/L, Na
2cO
350g/L, emulsifier op-10 0.5g/L, surplus is distilled water.
4., as claimed in claim 1 for the Electroless Nickel plating with Ultrasonic phosphorus method of NdFeB permanent magnet material, it is characterized in that:
Step c) in, consisting of of described acid pickling and rust removing liquid: 65%HNO
320ml/L, thiocarbamide 2g/L, surplus is distilled water.
5., as claimed in claim 1 for the Electroless Nickel plating with Ultrasonic phosphorus method of NdFeB permanent magnet material, it is characterized in that:
Steps d) in, regulate alkali plating solution pH value with NaOH, make plating solution pH >=12.
6., as claimed in claim 1 for the Electroless Nickel plating with Ultrasonic phosphorus method of NdFeB permanent magnet material, it is characterized in that:
Step e) in, regulate nickel plating phosphorus solution pH value with ammoniacal liquor, make nickel plating phosphorus solution pH=8 ~ 8.5.
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