CN103966636A - Ni-P-Mn electroplating solution and method for preparing Ni-P-Mn alloy coating on material surface - Google Patents
Ni-P-Mn electroplating solution and method for preparing Ni-P-Mn alloy coating on material surface Download PDFInfo
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Abstract
The invention discloses a Ni-P-Mn electroplating solution. The concentration of NiSO4*6H2O is 280-320 g/L, the concentration of nickel chloride is 40 g/L, the concentration of NaH2PO2*H2O is 30-50 g/L, the concentration of boric acid is 35-45 g/L, the concentration of manganese chloride is 5-30 g/L, the concentration of ammonium bifluoride is 15-25 g/L, and pH is regulated to be 3.0-5.0 by dilute sulfuric acid. The invention further discloses a method for preparing a Ni-P-Mn alloy coating on the material surface. The method comprises the following steps: pretreatment is performed on a workpiece through mechanical polishing, then oil is removed by a neutral solution, structural electroplating and heat treatment are performed, and the compact Ni-P-Mn alloy coating is obtained. According to the invention, manganese ions are added into the electroplating solution to improve the density and corrosion resistance of the coating, and the coating with high corrosion resistance and high density is prepared by combining the crystalline refining effect of post-plating heat treatment, the operation is simple, the energy consumption is low, and the coating is widely applied to the electronic industry.
Description
Technical field
The present invention relates to a kind of material surface anticorrosion process, particularly relate to the preparation technology of a kind of electroplate liquid and a kind of material surface coating, be applied to material surface preservative treatment technology field.
Background technology
Be in 1837 for the narration the earliest of electronickelling, Bird electrolysis single nickel salt or nickelous chloride several hours have obtained layer of metal nickel on platinum electrode.By 1840, first industrial nickel plating patent authorizing the Shore of Britain, he has determined nickelous nitrate electroplating solution.1916, Watter proposed famous watt type nickel plating system, and after this, nickel electroplating technology starts to enter the industry stage.Thereafter nickel field of electroplating has obtained develop rapidly, and process for electroplating of nickel-phosphorus alloy, nickel cobalt (alloy) plating etc. all progressively occur.Process for electroplating of nickel-phosphorus alloy, still used by Bo Lunna (A.Brenner) invention so far in nineteen forty-six.Nickel-phosphorus alloy coating has long service life, and coating is level and smooth, and glossiness is good, high hardness, wear resistance, solidity to corrosion and good catalytic performance.Therefore, be widely applied in various fields.But along with scientific progress, only just nickel phosphorus is electroplated the requirement that has been difficult to meet a lot of equipment, the raising requiring for coating erosion resistance, the requirement of density, all a kind of better nickel plating solution of active demand.
Nickel coating, for iron-based body, belongs to cathodic coating, has higher porosity, so adopt copper plate to make bottom more or adopt the method for multiple layer nickel plating to reduce hole.Reduce the hole of coating, can protect better matrix metal.By adding the element of some erosion resistances also can obtain the nickel alloy coating of compact structure.Manganese is a kind of transition metal, is canescence, and property is hard and crisp, is usually used in metallurgical industry in order to manufacture steel, or is used as desulfuration agent and Oxygen Scavenger.Manganese is abundant at China's reserves, has good application prospect.Manganese element has good solidity to corrosion, adds manganese in nickel plating solution, and the various performances of gained settled layer are apparently higher than pure nickel electrolytic coating.In watts nickel basal liquid, add manganese, contribute to obtain Magno coating careful, fine and close, high anti-corrosion.AtanassovA etc. think, in electroplating process, manganese is not to enter coating with the form of electrochemical redox, but enter with the form of similar composite deposite second-phase.So, after plating, just can make the crystal grain of coating more tiny by heat treated form, homogeneous is fine and closely woven.Up to the present, about the research of Magno galvanic deposit mainly concentrates on electrodeposition technology, the aspect such as coating performance, composition, pay close attention to less to its plating postheat treatment, traditional nickel coating or the physicochemical property of other alloy layers have much room for improvement, and how by selecting additive to improve corrosion resistance of coating and simplify aftertreatment technology also to become technical barrier urgently to be resolved hurrily.
Summary of the invention
In order to solve prior art problem, the object of the invention is to overcome the deficiency that prior art exists, it is the method that electroplate liquid and material surface are prepared Ni-P-Mn alloy layer that a kind of nickel phosphorus manganese is provided, in electroplate liquid, add mn ion to realize coating density, corrosion proof raising, in conjunction with the crystallization refining effect of plating postheat treatment, preparation height is anti-corrosion and the Ni-P-Mn alloy layer of high-compactness, coating total quality is high, electroplating operations technique is simple, and less energy-consumption is widely used in electronic industry.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A kind of nickel phosphorus manganese is electroplate liquid, and its formula is as follows:
NiSO
46H
2the concentration of O is 280-320 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 30-50 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 5-30g/L, and the concentration of ammonium bifluoride is 15-25g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 3.0-5.0.
As the preferred technical scheme of the present invention, nickel phosphorus manganese is that plating solution formula is as follows:
NiSO
46H
2the concentration of O is 295-310 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-45 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-20g/L, and the concentration of ammonium bifluoride is 15-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.5-5.0.
As the further preferred technical scheme of the present invention, nickel phosphorus manganese is that plating solution formula is as follows:
NiSO
46H
2the concentration of O is 295-305 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-42 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-18g/L, and the concentration of ammonium bifluoride is 21-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.8-5.0.
Adopt material surface that nickel phosphorus manganese of the present invention is electroplate liquid to prepare the method for Ni-P-Mn alloy layer, there are following steps:
A. the pre-treatment of surface of workpiece: adopt sand paper to polish to metal works, remove the oxide membranous layer of surface of workpiece, and metal works is carried out to mechanical polishing processing, make surface of workpiece there is mirror metal gloss; Preferably adopt sand papering surface of workpiece, the grinding turn of sand paper model successively: 600# → 1000# → 2000#, then by metal works polishing on metallographic-sample polisher, makes surface of workpiece have mirror metal gloss;
B. surface of workpiece oil removing: adopt acetone to carry out oil removing to the metal works of polishing through above-mentioned steps a;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is that the pH value of electroplate liquid is to 3.0-5.0 that the dilute sulphuric acid that is 5%-10% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 45-65 DEG C nickel phosphorus manganese, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2-3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, maintaining nickel phosphorus manganese is temperature of electroplating solution 45-65 DEG C, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 280-320 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 30-50 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 5-30g/L, and the concentration of ammonium bifluoride is 15-25g/L, preferably regulating nickel phosphorus manganese with dilute sulphuric acid is that the pH value of electroplate liquid is to 3.5-5.0, preferably maintaining nickel phosphorus manganese is temperature of electroplating solution 50-60 DEG C, preferably adopting nickel phosphorus manganese is the NiSO in electroplate liquid
46H
2the concentration of O is 295-310 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-45 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-20g/L, and the concentration of ammonium bifluoride is 15-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.5-5.0, preferably adopting nickel phosphorus manganese is the NiSO in electroplate liquid
46H
2the concentration of O is 295-305 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-42 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-18g/L, and the concentration of ammonium bifluoride is 21-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.8-5.0,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500-700 DEG C, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the present invention utilizes adding coating density, corrosion proof raising of mn ion, and the crystallization refining effect of plating postheat treatment, provides that a kind of novel height is anti-corrosion, high-compactness and the simple electronickelling preparation of manganese of operating procedure;
2. the corrosion resistance of coating that the present invention obtains strengthens, and density increases, and hardness obviously improves, and the present invention has less energy-consumption, high quality and simple to operation, and the series of advantages of excellent property is widely used in electronic industry;
3. the present invention has added mn ion and ammonium bifluoride in nickel-phosphorus alloy plating liquid, and the workpiece after electroplating is had to thermal treatment, makes electrolytic coating have hole little, density is high, reduce cathode hydrogen evolution, obviously improve the solidity to corrosion of deposition layer, and make coating mechanical property have obvious lifting.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment mono-:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: adopt sand papering surface of workpiece, the grinding turn of sand paper model is successively: 600# → 1000# → 2000#, remove the oxide membranous layer of surface of workpiece, then by metal works polishing on metallographic-sample polisher, make surface of workpiece there is mirror metal gloss;
B. surface of workpiece oil removing: adopt acetone to carry out oil removing to the metal works of polishing through above-mentioned steps a, fast except speed oil, except Special Circumstances, acetone does not generally corrode processed metal;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 3.5 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 57 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 57 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 280 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 40 g/L, the concentration of boric acid is 35/L, the concentration of Manganous chloride tetrahydrate is 5g/L, the concentration of ammonium bifluoride is 15g/L, surplus is water, when preparing nickel phosphorus manganese and being electroplate liquid, single nickel salt, nickelous chloride, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride are dissolved in water and mix formation electroplate liquid, sodium hypophosphite is dissolved in water, under the condition stirring, in the electroplate liquid that sodium hypophosphite solution is slowly poured into, and stir, add deionized water to prescribed volume to electroplate liquid, continue to stir, prepare electroplate liquid,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.The roughness of Ni-P-Mn alloy layer is 0.462 μ m, and microhardness HV is 351, and corrosion electric current density is 5.614 μ A/cm
2, corrosion potential-0.421 V, compares traditional nickel coating, is all improved.The present embodiment utilizes adding coating density, corrosion proof raising of mn ion, and the crystallization refining effect of plating postheat treatment, adopt high anti-corrosion, high-compactness and the simple electronickelling preparation of manganese of operating procedure to prepare Ni-P-Mn alloy layer at surface of workpiece, the corrosion resistance of coating obtaining is strong, good compactness, hardness is high.The present embodiment has less energy-consumption, high quality and series of advantages simple to operation, coating performance is good, is widely used in electronic industry.
embodiment bis-:
The present embodiment and embodiment mono-are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 3.8 of electroplate liquid that the dilute sulphuric acid that is 10% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 55 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 55 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 290 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 30 g/L, and the concentration of boric acid is 40/L, and the concentration of Manganous chloride tetrahydrate is 5g/L, and the concentration of ammonium bifluoride is 20g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 600 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment tri-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 4.2 of electroplate liquid that the dilute sulphuric acid that is 8% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 60 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 60 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2.5A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 300 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 50 g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 15g/L, and the concentration of ammonium bifluoride is 20g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 700 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment tetra-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 4.5 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 55 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 55 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 310 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 45 g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 20g/L, and the concentration of ammonium bifluoride is 15g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment five:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 4.0 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 63 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 63 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 320 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 35 g/L, and the concentration of boric acid is 40/L, and the concentration of Manganous chloride tetrahydrate is 30g/L, and the concentration of ammonium bifluoride is 25g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 600 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment six:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 3.8 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 65 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 65 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2.6A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 300 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 40 g/L, and the concentration of boric acid is 45/L, and the concentration of Manganous chloride tetrahydrate is 30g/L, and the concentration of ammonium bifluoride is 15g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 700 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment seven:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 3.0 of electroplate liquid that the dilute sulphuric acid that is 6% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 70 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 70 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2.5A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 285 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 32 g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 20g/L, and the concentration of ammonium bifluoride is 18g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment eight:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 5.0 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 45 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 45 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 295 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36 g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 12g/L, and the concentration of ammonium bifluoride is 24g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 600 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment nine:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 4.8 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 50 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 50 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 305g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 42g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 18g/L, and the concentration of ammonium bifluoride is 21g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 700 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment ten:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 3.4 of electroplate liquid that the dilute sulphuric acid that is 10% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 67 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 67 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 315g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 46g/L, and the concentration of boric acid is 35/L, and the concentration of Manganous chloride tetrahydrate is 18g/L, and the concentration of ammonium bifluoride is 16g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
embodiment 11:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, material surface is prepared the method for Ni-P-Mn alloy layer, has following steps:
A. the pre-treatment of surface of workpiece: identical with embodiment mono-;
B. surface of workpiece oil removing: identical with embodiment mono-;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is the pH value to 4.6 of electroplate liquid that the dilute sulphuric acid that is 5% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 61 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be 61 DEG C of temperature of electroplating solution, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, Accelerative mass transfer process, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 300g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36g/L, and the concentration of boric acid is 41/L, and the concentration of Manganous chloride tetrahydrate is 10g/L, and the concentration of ammonium bifluoride is 18g/L, and surplus is water,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 600 DEG C, makes the crystal grain in Ni-P-Mn alloy layer more fine and closely woven, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
The present embodiment Ni-P-Mn alloy layer that surface of workpiece is obtained carries out solidity to corrosion, electro-chemical test that alkali resistance is relevant, and the performance test results of the Ni-P-Mn alloy layer of surface of workpiece is referring to table 1.
As seen from Table 1, the above embodiment of the present invention preparation has all obtained the Ni-P-Mn alloy layer of high-quality, has good corrosion resistance nature, simple to operate.Wherein, the Ni-P-Mn alloy layer of preparing at embodiment tetra-and embodiment eight obviously reduces than the roughness of the Ni-P-Mn alloy layer of preparation in embodiment mono-, embodiment bis-, embodiment tri-, embodiment five, embodiment six, embodiment seven, embodiment ten and embodiment 11, and the hardness of Ni-P-Mn alloy layer is obviously improved, corrosion resistant chemical property obviously improves; And Ni-P-Mn alloy layer prepared by embodiment nine is lower than the roughness of the Ni-P-Mn alloy layer of preparing at other embodiment, hardness is higher, corrosion resistant chemical property is more excellent.
It is the solidity to corrosion that electroplate liquid improves surface of workpiece that above-described embodiment adopts nickel phosphorus manganese, by surperficial mechanical polishing method, metal works is carried out to mechanical pretreatment, put it under mesophilic condition and in acetone, carry out neutral solution oil removing, and remove the dirt settling residuing on specimen surface, to improve cleanliness factor and the quality of coating on plating piece surface.Then structure is electroplated and thermal treatment, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.Through test, in the above-described embodiments Ni-P-Mn alloy layer after treatment hardness and anti-corrosion aspect be all improved largely, effectively improve the corrosion resisting property of Ni-P-Mn alloy layer, improve work-ing life of coating, simple to operate, solidity to corrosion is high.
Above the embodiment of the present invention is illustrated; but the invention is not restricted to above-described embodiment; can also make multiple variation according to the object of innovation and creation of the present invention; the change made under all spirit according to technical solution of the present invention and principle, modification, substitute, combination, simplify; all should be equivalent substitute mode; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept that nickel phosphorus manganese of the present invention is electroplate liquid and the material surface method of preparing Ni-P-Mn alloy layer, all belong to protection scope of the present invention.
Claims (9)
1. nickel phosphorus manganese is an electroplate liquid, it is characterized in that, plating solution formula is as follows:
NiSO
46H
2the concentration of O is 280-320 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 30-50 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 5-30g/L, and the concentration of ammonium bifluoride is 15-25g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 3.0-5.0.
2. nickel phosphorus manganese is electroplate liquid according to claim 1, it is characterized in that:
NiSO
46H
2the concentration of O is 295-310 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-45 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-20g/L, and the concentration of ammonium bifluoride is 15-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.5-5.0.
3. nickel phosphorus manganese is electroplate liquid according to claim 2, it is characterized in that:
NiSO
46H
2the concentration of O is 295-305 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-42 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-18g/L, and the concentration of ammonium bifluoride is 21-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.8-5.0.
4. adopting nickel phosphorus manganese described in claim 1 is the method that the material surface of electroplate liquid is prepared Ni-P-Mn alloy layer, it is characterized in that having following steps:
A. the pre-treatment of surface of workpiece: adopt sand paper to polish to metal works, remove the oxide membranous layer of surface of workpiece, and metal works is carried out to mechanical polishing processing, make surface of workpiece there is mirror metal gloss;
B. surface of workpiece oil removing: adopt acetone to carry out oil removing to the metal works of polishing through above-mentioned steps a;
C. preparation of coatings: adopting nickel phosphorus manganese is electroplate liquid, it is that the pH value of electroplate liquid is to 3.0-5.0 that the dilute sulphuric acid that is 5%-10% by mass concentration regulates nickel phosphorus manganese, then be that electroplate liquid is heated to 45-65 DEG C nickel phosphorus manganese, and to maintain nickel phosphorus manganese be temperature of electroplating solution 45-65 DEG C, to put into nickel phosphorus manganese through above-mentioned steps b metal works after treatment is again electroplate liquid, using metal works as negative electrode, using nickel metal as negative electrode, control cathode current density is 2-3A/dm, be that electroplate liquid carries out induction stirring to nickel phosphorus manganese, nickel phosphorus manganese is that main solute component in electroplate liquid is by single nickel salt, nickelous chloride, sodium hypophosphite, boric acid, Manganous chloride tetrahydrate and ammonium bifluoride composition, wherein NiSO
46H
2the concentration of O is 280-320 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 30-50 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 5-30g/L, and the concentration of ammonium bifluoride is 15-25g/L,
D. coating thermal treatment: metal works, after above-mentioned steps c has electroplated, is heat-treated at 500-700 DEG C, finally obtains fine and close Ni-P-Mn alloy layer at surface of workpiece.
5. material surface is prepared the method for Ni-P-Mn alloy layer according to claim 4, it is characterized in that: in above-mentioned steps c, regulating nickel phosphorus manganese with dilute sulphuric acid is that the pH value of electroplate liquid is to 3.5-5.0.
6. the method for preparing Ni-P-Mn alloy layer according to material surface described in claim 4 or 5, is characterized in that: in above-mentioned steps c, maintaining nickel phosphorus manganese is temperature of electroplating solution 50-60 DEG C.
7. prepare the method for Ni-P-Mn alloy layer according to material surface described in claim 4 or 5, it is characterized in that, in above-mentioned steps a, adopt sand papering surface of workpiece, the grinding turn of sand paper model is successively: 600# → 1000# → 2000#, then by metal works polishing on metallographic-sample polisher, make surface of workpiece there is mirror metal gloss.
8. the method for preparing Ni-P-Mn alloy layer according to material surface described in claim 4 or 5, is characterized in that: nickel phosphorus manganese is the NiSO in electroplate liquid
46H
2the concentration of O is 295-310 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-45 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-20g/L, and the concentration of ammonium bifluoride is 15-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.5-5.0.
9. material surface is prepared the method for Ni-P-Mn alloy layer according to claim 8, it is characterized in that: nickel phosphorus manganese is the NiSO in electroplate liquid
46H
2the concentration of O is 295-305 g/L, and the concentration of nickelous chloride is 40 g/L, NaH
2pO
2h
2the concentration of O is 36-42 g/L, and the concentration of boric acid is 35-45g/L, and the concentration of Manganous chloride tetrahydrate is 12-18g/L, and the concentration of ammonium bifluoride is 21-24g/L, and adopting dilute sulphuric acid to regulate electroplate liquid pH is 4.8-5.0.
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| CN106400069A (en) * | 2016-09-12 | 2017-02-15 | 国家电网公司 | Anti-corrosion method for copper or copper alloy power grid grounding device in acid soil |
| CN108411343A (en) * | 2018-04-10 | 2018-08-17 | 上海大学 | A kind of plating cobalt tungsten manganese high-strength steel and its preparation method and application |
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| KR20070087723A (en) * | 2005-07-29 | 2007-08-29 | 주식회사 포스코 | Galvannealed steel sheet having excellent formability and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106400069A (en) * | 2016-09-12 | 2017-02-15 | 国家电网公司 | Anti-corrosion method for copper or copper alloy power grid grounding device in acid soil |
| CN106400069B (en) * | 2016-09-12 | 2019-06-07 | 国家电网公司 | A kind of anti-corrosion method of copper or copper alloy power grid earthing or grounding means in acid soil |
| CN108411343A (en) * | 2018-04-10 | 2018-08-17 | 上海大学 | A kind of plating cobalt tungsten manganese high-strength steel and its preparation method and application |
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