CN106507857B - Cobalt block nickel plating technology - Google Patents
Cobalt block nickel plating technologyInfo
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- CN106507857B CN106507857B CN200810077759.4A CN200810077759A CN106507857B CN 106507857 B CN106507857 B CN 106507857B CN 200810077759 A CN200810077759 A CN 200810077759A CN 106507857 B CN106507857 B CN 106507857B
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- cobalt block
- plating
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Abstract
The present invention relates to one kind is in cobalt block plating nickel on surface technique, the technique is etched, is activated to cobalt block using the method for anode electrolysis before the plating of cobalt block, and, for hydrochloric acid solution, negative electrode is titanium plate or stereotype, and anode is cobalt block for the etching that adopts, activating solution；Method of barrel electroplating, plating solution is adopted to adopt watt type plating solution when cobalt block is electroplated, salt provides nickel ion based on nickel sulfate, anode is nickel plate, and negative electrode is cobalt block, and barrel plating power supply is using dipulse direct current electrode position power supply.Present invention process makes that the nickel dam adhesive strength plated by cobalt block surface is high, roughness is little, impurity content is low, uniformity good.
Description
Technical field
The present invention relates to cobalt surface treatment technology of material, and in particular to one kind is in cobalt block plating nickel on surface
Technique.
Background technology
Cobalt block is generally made with powder metallurgical technique, occurs that cobalt comes off in use, but
Become cobalt radioactive source after irradiation, never allow cobalt to come off, therefore need to electroplate in cobalt material surface
Certain thickness metallic nickel is protected.Nickel coating on cobalt material surface because its use special
Environment and purposes, coating should have adhesive strength height, roughness is little, uniformity is good, impurity element
The features such as content is few.Report about cobalt block nickel plating technology is had no at present.
Content of the invention
It is an object of the invention to provide a kind of adhere to can the nickel dam that plated on cobalt block surface
Intensity is high, the cobalt block nickel plating technology that roughness is little, impurity content is low, uniformity is good.
Realize the technical scheme of the object of the invention：A kind of cobalt block nickel plating technology, its are electroplated in cobalt block
The front method using anode electrolysis is etched, activates to cobalt block, the etching of employing, activating solution
For the hydrochloric acid solution of 50～250ml/L, negative electrode is titanium plate or stereotype, and anode is cobalt block, negative electrode
Distance with anode is 20～150mm, and current density is 0.9～2A/dm2, etching, activation
Temperature is 15～30 DEG C, and etching period is 60～90s, and soak time is 5～15s；In cobalt block
Method of barrel electroplating is adopted during plating, will cobalt block mix with filler and be put in cylinder, reality in the plating solution
Existing barrel plating, plating solution adopt watt type plating solution, and based on nickel sulfate, salt provides nickel ion, and anode is
Nickel plate, negative electrode are cobalt block, and barrel plating liquid temp is 45～65 DEG C, and the barrel plating time is 30～60min,
Barrel plating power supply using dipulse direct current electrode position power supply, after plating timing, forward current opens 5～
Reversing the current is opened after 10min again, and forward current density is 0.3～1A/dm2, reversing the current is close
Spend for 0.02～0.1A/dm2.
Cobalt block nickel plating technology as above, its in cobalt block barrel plating, filler used be diameter 3～
The spherosome of 5mm, ordinary carbon steel of the spherosome material for plating nickel on surface；Cobalt block length side
Be (6～10) to the ratio of size and filler diameter: 1, the quantity ratio of cobalt block and filler for (8～
10): (5000～7000)；Drum rotation speed is 18～25 revs/min；Described bath composition
Including concentration is the NiSO of 260～300g/L4·6H2O, concentration are 7～40g/L's
NiCl2·6H2O, concentration are the H of 30～40g/L3BO3, concentration is 0.05～0.1g/L's
Lauryl sodium sulfate, bath pH value are 4.6～5.8.
Cobalt block nickel plating technology as above, its are removed to cobalt block before cobalt block is etched, activated
Oil, will cobalt block be put into 10～15min in the cleaning agent that temperature is 60～90 DEG C, then take out
Cobalt block, is cleaned with water, then is dried up.
Cobalt block nickel plating technology as above, which is etched in cobalt block, after activation, before being electroplated
Ultrasonic wave is cleaned, ultrasonic wave 0.5～1min of scavenging period.
As above cobalt block nickel plating technology, which cleans cobalt block after cobalt block barrel plating with water, then dries up.
Effect of the invention is that：The present invention processes cobalt block using etching, activation method, then
Using method of barrel electroplating in cobalt block plating nickel on surface, the nickel coating uniformity on its gained cobalt block surface is good,
Adhesive strength is high, surface roughness is little, impurity content is low, good combination property.Present invention process
Nickel plating speed is fast, thickness of coating is easy to control, apparatus and process is simple and convenient to operate, low cost,
Environmental pollution is little, safety, easily uses aborning.
Specific embodiment
Cobalt block nickel plating technology of the present invention is made furtherly with reference to specific embodiment
Bright.
Embodiment 1
(1) cobalt block oil removing：Metal cleaner (commercially available, the ProductName that cobalt block is put into 80 DEG C
Referred to as cleaning agent, label JB-4322-4323-86) in, 10min is soaked, cobalt block is then taken out,
Cleaned with water, then dried up.
There is the cleaning agent aqueous solution emulsification to be deoiled effect with saponification, in order to remove cobalt block surface oil
Dirty.
(2) etching of cobalt block, activation：Activation is etched to cobalt block using anode electrochemical method,
The hydrochloric acid solution of etching activating solution used for 50ml/L, negative electrode are titanium plate, and anode is cobalt block,
Negative electrode is 20mm with the distance of anode, and current density is 2A/dm2, etching activation temperature is 25
DEG C, etching period is 60s, and soak time is 10s.
After etched, activation, cobalt block surface energy obtains larger asperity, and reaches
The state of activation, so that improve the adhesion of nickel coating and matrix.After etching activation, cobalt block surface is thick
Rugosity is less than 0.4 μm, and anode reaction is：Co-2e-Co2+.Hydrochloric acid is main in etching activating solution
Electric action to be risen, while there is chemical reaction with cobalt block, plays etching action.
(3) ultrasonic wave cleaning：Using ultrasonic wave clean cobalt block, ultrasonic wave scavenging period 0.5min,
Frequency is 40kHz, and power is 1kW.
Cleaned by ultrasonic wave, the superfines that cobalt block surface attaches can be removed, further improved
Coating and the adhesion of cobalt block.
(4) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 45 DEG C, the barrel plating time be 60min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 10min again in source
Reversing the current, forward current density are 0.3A/dm2, reverse current density is 0.05A/dm2.
Spherosome of the filler used for diameter 3mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 6: 1, the number of cobalt block and filler
Amount is than being 8: 5000；Drum rotation speed is 25 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 260g/L4·6H2O,
NiCl of the concentration for 7g/L2·6H2O, H of the concentration for 30g/L3BO3, concentration is 0.05g/L
Lauryl sodium sulfate, bath pH value be 4.6～5.0.
Method of the nickel plating using barrel plating, it is to avoid the concentration polarization of solution, make cobalt block nearby nickel from
The concentration of son is supplemented in time；Bath stability, is easily controlled, and valid density change is little, plating
Layer purity is high, and the particularly impurity content such as cobalt is few.
(5) cobalt block cleaning：Cleaned with water after cobalt block barrel plating, then dried up.
The present invention is etched, is activated using the method for anode electrolysis before plating to cobalt block, is made
Cobalt block surface homogeneous corrosion falls 2-4 μm of thickness, obtains larger asperity and higher
Surface-active.By using certain density hydrochloric acid solution, and using insoluble Titanium or lead
Used as negative electrode, cobalt block is used as anode, and makes the distance controlling of cathode and anode within the specific limits,
Carry out chemical etching and activation.While ensureing that cobalt block surface roughness is less than 0.4 μm,
Larger asperity is obtained, and the uniform cobalt block surface-active of etching is higher, and through super
Sound wave cleaning removes the loose powder that cobalt material surface is produced because of activation, coating is obtained most preferably
Adhesive strength.
During cobalt block barrel plating when current lead-through, activation polarization increases, the nickel near negative electrode
Ion is fully deposited, and coating crystallization is careful, bright.When forward current turn-off reversal electric current is led
When logical, the nickel ion near negative electrode returns to initial concentration again, eliminates the concentration polarization in cathodic region
Change；Reverse pulse current also has a sharp angle effect, thus the burr of dissolved cobalt block surface nickel coating and
The thickness coating of sharp corner, improves the thickness distribution of coating and makes nickel coating thickness more uniform,
And make plating piece surface be constantly in the state of activation, high-adhesion uniformity can be obtained preferable
Plated film.
Nickel plating solution salt based on nickel sulfate, and containing anode activation agent and buffering component, lead to
The control temperature of plating solution, pH value, forward and reverse electric current of the pulse power is crossed, with certain plating
The nickel coating that method is obtained is fine and close, bright, uniform, and the impurity content of the cobalt in nickel dam is equal
Can control in claimed range.Nickel dam has good adhesive strength with cobalt-based body.Hold with film forming
Easily, film forming speed is fast, film thickness is easily controlled, equipment and process is simple, environmental pollution are little,
The advantage that production security is high, integrated cost is low, easily use aborning.
Embodiment 2
(1) cobalt block oil removing：Cobalt block is put in 90 DEG C of metal cleaner, 10min is soaked,
Cobalt block is then taken out, is cleaned with water, then dried up.
(2) the etching activation of cobalt block：Cobalt block is etched, is activated using anode electrochemical method,
Etching used, activating solution for 100ml/L hydrochloric acid solution, negative electrode is titanium plate, and anode is cobalt
Block, negative electrode are 40mm with the distance of anode, and current density is 0.9A/dm2, etching, activation
Temperature is 27 DEG C, and etching period is 90s, and soak time is 15s.
(3) ultrasonic wave cleaning：Using ultrasonic wave clean cobalt block, ultrasonic wave scavenging period 1min,
Frequency is 40kHz, and power is 1kW.
(4) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 50 DEG C, the barrel plating time be 40min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 5min again in source
Reversing the current, forward current density are 1A/dm2, reverse current density is 0.1A/dm2.
Spherosome of the filler used for diameter 4mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 10: 1, cobalt block and filler
Quantity ratio is 8: 7000)；Drum rotation speed is 18 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 300g/L4·6H2O,
NiCl of the concentration for 40g/L2·6H2O, H of the concentration for 40g/L3BO3, concentration is 0.1g/L
Lauryl sodium sulfate, bath pH value be 5.0～5.8.
(5) cobalt block cleaning：Washed with flowing after cobalt block barrel plating, deionization is washed, anhydrous
Ethanol dehydration, drying.
Embodiment 3
(1) cobalt block oil removing：Cobalt block is put in 85 DEG C of metal cleaner, 12min is soaked,
Cobalt block is then taken out, is dehydrated, dried with flowing washing, deionization washing, absolute ethyl alcohol.
(2) the etching activation of cobalt block：Respectively cobalt block is etched using anode electrochemical method,
Activation process, etching used, activating solution for 150ml/L hydrochloric acid solution, negative electrode is stereotype,
Anode is cobalt block, and negative electrode is 100mm with the distance of anode, and current density is 1A/dm2, erosion
It is 30 DEG C to carve activation temperature, and etching period is 60s, and soak time is 15s.
(3) ultrasonic wave cleaning：Using ultrasonic wave clean cobalt block, ultrasonic wave scavenging period 0.8min,
Frequency is 40kHz, and power is 1kW.
(4) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 65 DEG C, the barrel plating time be 30min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 7min again in source
Reversing the current, forward current density are 0.8A/dm2, reverse current density is 0.02A/dm2.
Spherosome of the filler used for diameter 4mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 8: 1, cobalt block and filler
Quantity ratio is 10: 5000；Drum rotation speed is 16 revs/min.
Watt type bath composition used includes, NiSO of the concentration in 280g/L4·6H2O,
NiCl of the concentration for 20g/L2·6H2O, H of the concentration for 35g/L3BO3, concentration is 0.08g/L
Lauryl sodium sulfate, bath pH value is 4.6.
(5) cobalt block cleaning：Washed with flowing after cobalt block barrel plating, deionization is washed, anhydrous
Ethanol dehydration, drying.
Embodiment 4
(1) cobalt block oil removing：Cobalt block is put in 80 DEG C of metal cleaner, 10min is soaked,
Cobalt block is then taken out, is cleaned with water, then dried up.
(2) the etching activation of cobalt block：Cobalt block is etched, is activated using anode electrochemical method,
Etching used, activating solution for 50ml/L hydrochloric acid solution, negative electrode is titanium plate, and anode is cobalt
Block, negative electrode are 20mm with the distance of anode, and current density is 0.9A/dm2, etching activation temperature
Spend for 25 DEG C, etching period is 70s, and soak time is 5s.
(3) ultrasonic wave cleaning：Using ultrasonic wave clean cobalt block, ultrasonic wave scavenging period 1min,
Frequency is 40kHz, and power is 1kW.
(4) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 45 DEG C, the barrel plating time be 30min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 5min again in source
Reversing the current, forward current density are 0.3A/dm2, reverse current density is 0.02A/dm2.
Spherosome of the filler used for diameter 3mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 6: 1, cobalt block and filler
Quantity ratio is 9: 7000；Drum rotation speed is 15 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 260g/L4·6H2O,
NiCl of the concentration for 7g/L2·6H2O, H of the concentration for 30g/L3BO3, concentration is 0.05g/L
Lauryl sodium sulfate, bath pH value is 4.6.
(5) cobalt block cleaning：Cleaned with water after cobalt block barrel plating, then dried up.
Embodiment 5
(1) cobalt block oil removing：Cobalt block is put in 90 DEG C of metal cleaner, 15min is soaked,
Cobalt block is then taken out, is cleaned with water, then dried up.
(2) the etching activation of cobalt block：Cobalt block is etched, is activated using anode electrochemical method,
Etching used, activating solution for 250ml/L hydrochloric acid solution, negative electrode is stereotype, and anode is cobalt
Block, negative electrode are 150mm with the distance of anode, and current density is 2A/dm2, etching activation temperature
Spend for 30 DEG C, etching period is 65s, and soak time is 12s.
(3) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 55 DEG C, the barrel plating time be 60min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 10min again in source
Reversing the current, forward current density are 1A/dm2, reverse current density is 0.1A/dm2.
Spherosome of the filler used for diameter 5mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 10: 1, cobalt block and filler
Quantity ratio is 9: 6500；Drum rotation speed is 18 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 300g/L4·6H2O,
NiCl of the concentration for 40g/L2·6H2O, H of the concentration for 40g/L3BO3, concentration is 0.1g/L
Lauryl sodium sulfate, bath pH value is 5.8.
(4) cobalt block cleaning：Cleaned with water after cobalt block barrel plating, then dried up.
Embodiment 6
(1) the etching activation of cobalt block：Cobalt block is etched using anode electrochemical method, lived
Change, etching used, activating solution for 100ml/L hydrochloric acid solution, negative electrode is titanium plate, anode
For cobalt block, negative electrode is 80mm with the distance of anode, and current density is 1.4A/dm2, etching work
It is 25 DEG C to change temperature, and etching period is 80s, and soak time is 7s.
(2) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating temperature be 55 DEG C, the barrel plating time be 40min, barrel plating power supply
Using dipulse direct current electrode position power supply, after electroplating timing, forward current opens 7min, then again
Reversing the current is opened, forward current density is 0.4A/dm2, reverse current density is 0.04A/dm2.
Spherosome of the filler used for diameter 4mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 7: 1, cobalt block and filler
Quantity ratio is 9: 5500；Drum rotation speed is 17 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 280g/L4·6H2O,
NiCl of the concentration for 20g/L2·6H2O, H of the concentration for 35g/L3BO3, concentration is 0.07g/L
Lauryl sodium sulfate, bath pH value is 4.8.
Embodiment 7
(1) cobalt block oil removing：Cobalt block is put in 85 DEG C of metal cleaner, 12min is soaked,
Cobalt block is then taken out, is cleaned with water, then dried up.
(2) the etching activation of cobalt block：Respectively cobalt block is etched using anode electrochemical method,
Activation, etching used, activating solution for 150ml/L hydrochloric acid solution, negative electrode is stereotype, sun
The distance of extremely cobalt block, negative electrode and anode is 120mm, and current density is 1.6A/dm2, etching
Activation temperature is 30 DEG C, and etching period is 110s, and soak time is 110s.
(4) cobalt block barrel plating：Method of barrel electroplating is adopted when cobalt block is electroplated, will cobalt block and filler
Mixing is put in cylinder, realizes that barrel plating, plating solution using watt type plating solution, anode are in the plating solution
Nickel plate, negative electrode be cobalt block, barrel plating liquid temp be 60 DEG C, the barrel plating time be 50min, barrel plating electricity
Using dipulse direct current electrode position power supply, after plating timing, forward current is opened after opening 9min again in source
Reversing the current, forward current density are 0.9A/dm2, reverse current density is 0.07A/dm2.
Spherosome of the filler used for diameter 3mm, the spherosome material are general for plating nickel on surface
Logical carbon steel；The ratio of cobalt block length direction size and filler diameter is 9: 1, cobalt block and filler
Quantity ratio is 10: 7000；Drum rotation speed is 16 revs/min.
Watt type bath composition used includes that concentration is the NiSO of 290g/L4·6H2O,
NiCl of the concentration for 30g/L2·6H2O, H of the concentration for 35g/L3BO3, concentration is 0.08g/L
Lauryl sodium sulfate, bath pH value is 5.2.
(5) cobalt block cleaning：Washed with flowing after cobalt block barrel plating, deionization is washed, anhydrous
Ethanol dehydration, drying.
Claims (5)
1. a kind of cobalt block nickel plating technology, it is characterised in that：The technique is adopted before the plating of cobalt block
The method of anode electrolysis is etched, activates to cobalt block, the etching that adopts, activating solution for 50～
The hydrochloric acid solution of 250m1/L, negative electrode are titanium plate or stereotype, and anode is cobalt block, negative electrode and anode
Distance be 20～150mm, current density be 0.9～2A/dm2, etching, activation temperature are
15～30 DEG C, etching period is 60～90s, and soak time is 5～15s；When cobalt block is electroplated
Using method of barrel electroplating, will cobalt block mix with filler and be put in cylinder, realize barrel plating in the plating solution,
Plating solution adopts watt type plating solution, and based on nickel sulfate, salt provides nickel ion, and anode is nickel plate, cloudy
Extremely cobalt block, barrel plating liquid temp are 45～65 DEG C, and the barrel plating time is 30～60min, barrel plating electricity
Source adopts dipulse direct current electrode position power supply, after plating timing, after forward current opens 5～10min
Reversing the current is opened again, and forward current density is 0.3～1A/dm2, reverse current density be 0.02～
0.1A/dm2.
2. cobalt block nickel plating technology according to claim 1, it is characterised in that：In cobalt block
During barrel plating, spherosome of the filler used for 3～5mm of diameter, the spherosome material are plated surface
The ordinary carbon steel of nickel；The ratio of cobalt block length direction size and filler diameter is 6～10: 1, cobalt
Block is 8～10: 5000～7000 with the quantity ratio of filler；Drum rotation speed is 18～25 revs/min
Clock；Described bath composition includes that concentration is the NiSO of 260～300g/L4·6H2O is dense
Spend the NiCl for 7～40g/L2·6H2O, concentration are the H of 30～40g/L3BO3, concentration is
The lauryl sodium sulfate of 0.05～0.1g/L, bath pH value are 4.6～5.8.
3. cobalt block nickel plating technology according to claim 1 and 2, it is characterised in that：?
Cobalt block etching, activation before oil removing is carried out to cobalt block, will cobalt block be put into temperature be 60～90 DEG C
Cleaning agent in 10～15min, then take out cobalt block, cleaned with water, then dry up.
4. cobalt block nickel plating technology according to claim 1 and 2, it is characterised in that：?
After the etching of cobalt block, activation, carry out electroplating front ultrasonic wave cleaning, ultrasonic wave scavenging period 0.5～
1min.
5. cobalt block nickel plating technology according to claim 1 and 2, it is characterised in that：?
Cobalt block is cleaned with water after cobalt block barrel plating, then is dried up.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810077759.4A CN106507857B (en) | 2008-11-25 | 2008-11-25 | Cobalt block nickel plating technology |
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| CN200810077759.4A CN106507857B (en) | 2008-11-25 | 2008-11-25 | Cobalt block nickel plating technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108221015A (en) * | 2017-12-28 | 2018-06-29 | 中核北方核燃料元件有限公司 | A kind of medical cobalt source cobalt pellet nickel plating process |
| CN110747493A (en) * | 2018-07-24 | 2020-02-04 | 上海睿福有色金属有限公司 | Method for producing electrolytic nickel material by barrel plating method |
-
2008
- 2008-11-25 CN CN200810077759.4A patent/CN106507857B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108221015A (en) * | 2017-12-28 | 2018-06-29 | 中核北方核燃料元件有限公司 | A kind of medical cobalt source cobalt pellet nickel plating process |
| CN110747493A (en) * | 2018-07-24 | 2020-02-04 | 上海睿福有色金属有限公司 | Method for producing electrolytic nickel material by barrel plating method |
| CN110747493B (en) * | 2018-07-24 | 2022-07-22 | 上海睿福有色金属有限公司 | Method for producing electrolytic nickel material by barrel plating method |
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