CN107858723A - A kind of method of Electroplating from Molten Salts Ni Yb alloy-layer modified metal nickel surfaces - Google Patents
A kind of method of Electroplating from Molten Salts Ni Yb alloy-layer modified metal nickel surfaces Download PDFInfo
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- CN107858723A CN107858723A CN201711098026.4A CN201711098026A CN107858723A CN 107858723 A CN107858723 A CN 107858723A CN 201711098026 A CN201711098026 A CN 201711098026A CN 107858723 A CN107858723 A CN 107858723A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
Abstract
The present invention relates to metallic nickel process for modifying surface, specifically a kind of method of Electroplating from Molten Salts Ni Yb alloy-layer modified metal nickel surfaces.The present invention comprises the following steps：(1) raw material, (2) anhydrous CaF are matched2LiF basic electrolytes purify, (3) Molten Salt Electroplating, (4) surface treatment.Using melten salt electriochemistry method directly by oxide raw material (Yb2O3, NiO) in nickel metal surface deposit Ni Yb alloy layers, can solve yield, energy consumption and Cost Problems well, and environment-friendly.By controlling electroplating technology ginseng to form 0.5~2mm Ni Yb alloy layers in nickel metal surface, so as to significantly improve the combination properties such as its surface machinery, electricity, magnetic.
Description
Technical field
The present invention relates to metallic nickel process for modifying surface, specifically a kind of Electroplating from Molten Salts Ni-Yb alloy-layers modified metal nickel table
The method in face.
Background technology
Yb is the relatively sufficient heavy rare earth element (crustal abundance 3.3ppm) of resource, and its application field more is confined to its light
Learn characteristic.In recent years, many studies have shown that Yb is very wide in the application prospect of non-ferrous alloy structure and field of functional materials
It is wealthy, it is accordingly required in particular to, it is noted that the heavy rare earth elements such as Yb are added in nickel and its alloy can significantly improve the electricity, magnetic or machine of alloy
Tool performance, there is unique modification and Strengthening and Toughening effect, special role can be produced to the magnetic property of nickel alloy.Certainly, permitted
It is multi-field, it is necessary to nickel metallic surface performance is very superior, closed therefore, it is possible to form certain thickness Ni-Yb in nickel metal surface
Gold plate, it will significantly improve electricity, magnetic, machinery, the corrosion resistance of nickel metal surface.Because metal Yb mainly passes through gold
Belong to La vacuum reductions Yb2O3Obtain, this technique production capacity is low, equipment is numerous and diverse, operation is discontinuous, and energy consumption is big and production cost is high, system
About its development.Therefore, the cost for forming Ni-Yb alloy layers in nickel metal surface by simple metal Yb vacuum evaporations can enter one
Step improves.
The content of the invention
It is an object of the present invention to provide a kind of method of Electroplating from Molten Salts Ni-Yb alloy-layers modified metal nickel surface, it drop energy consumption, into
This is low and environment-friendly, is by the method for electroreduction mode Ni-Yb alloy-layer modified metal nickel surfaces in molten salt system.
Technical scheme：A kind of method of Electroplating from Molten Salts Ni-Yb alloy-layers modified metal nickel surface, including following step
Suddenly：
(1) raw material are matched：
With anhydrous CaF2, electrolyte based on LiF, Yb2O3, NiO be Ni-Yb alloy layers donor material；
Ratio requirement：
Anhydrous CaF2, LiF mixtures be system supporting electrolyte, account for Electroplating from Molten Salts system material mass percentage composition for 95~
97%, remaining is Yb2O3And NiO, and CaF2:LiF mol ratio=1:1, Yb2O3:NiO mol ratio=1:4；
(2) anhydrous CaF2- LiF basic electrolytes purify：
By the anhydrous CaF in step (1)2, LiF be sufficiently mixed, melt under 850 DEG C~900 DEG C nitrogen protective conditions of temperature
Change, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, in 0.6~1.2V of voltage, 0.2~0.6A/cm of current density2Bar
Preelectrolysis is carried out under part, the time is 0.5~1h；Then, the high pure nitrogen stirring melt of 2~6 times of fused salt volumes is passed through, and true
1h is incubated at 100~500Pa of reciprocal of duty cycle, 800 DEG C of temperature, removes dross on surface of fusant；
(3) Molten Salt Electroplating：
To the CaF of step (2) purification2- LiF basic electrolytes melt leads to argon gas protection, in 900~950 DEG C of temperature, voltage
3.5~3.9V, 0.7~0.9A/cm of current density2Under the conditions of, taking-up negative electrode is cooled to room in argon gas after electroplating 2.5~3.5h
Temperature, negative electrode are metal Ni substrate, and anode is high purity graphite；
(4) it is surface-treated：
Nickel cathode surface after step (3) Molten Salt Electroplating is removed into particle and burr, and cleaned with 0.1mol/L phosphoric acid,
Through 90 DEG C of drying 2h after being cleaned again with distilled water.
Major control condition and foundation：
1、CaF2The purification of-LiF media bases ensures influence of other impurity to coating in elimination system, relies primarily on pre- electricity
Solution reaction forms impurity product and is by nitrogen gas stirring, absorption, floating, major control condition：850 DEG C~900 DEG C of temperature, tungsten
Matter negative electrode, glass carbon anode, 0.6~1.2V of voltage, 0.2~0.6A/cm of current density2, 0.5~1h of electrolysis time.
2nd, ensure that good Ni-Yb alloy-layers need to strictly control Electroplating from Molten Salts condition：900~950 DEG C of temperature, voltage 3.5~
3.9V, 0.7~0.9A/cm of current density2, cathodic metal Ni substrate, anode is high purity graphite, 2.5~3.5h of electroplating time.
Using melten salt electriochemistry method directly by oxide raw material (Yb2O3, NiO) nickel metal surface deposit Ni-Yb alloys
Coating, can solve yield, energy consumption and Cost Problems well, and it is environment-friendly.By controlling electroplating technology ginseng in nickel metal watch
Face forms 0.5~2mm Ni-Yb alloy layers, so as to significantly improve the combination properties such as its surface machinery, electricity, magnetic.
Embodiment
Embodiment 1：By CaF2, LiF (mol ratio CaF2:LiF=1:1) it is sufficiently mixed, in 850 DEG C of temperature, nitrogen ceiling
Melt under part, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, voltage 0.6V, current density 0.2A/cm2Under the conditions of it is pre-
It is electrolysed 0.5h；Then, the high pure nitrogen stirring melt of 2 times of fused salt volumes is passed through, then at vacuum 500Pa, 800 DEG C of temperature
1h is incubated, removes dross on surface of fusant.In the CaF of purification2- LiF media bases (mol ratio CaF2:LiF=1:1, quality percentage
Content is 97%) in melt, adds Yb2O3- NiO mixed powders (Yb2O3:NiO=1:4, mol ratio), lead to argon gas protection, temperature
900 DEG C, voltage 3.5V, current density 0.7A/cm2, negative electrode be metal Ni substrate, anode is high purity graphite, electroplating time 2.5h
It is proposed that negative electrode is cooled to room temperature (25 DEG C) in argon gas afterwards.Nickel cathode surface after plating after removing particle and burr processing,
Phosphoric acid cleaning through 0.1mol/L, after testing, can be in nickel metal surface shape through 90 DEG C of drying 2h after then being cleaned with distilled water
Into 0.52mm Ni-Yb alloy layers, its surface comprehensive performance is significantly improved.
Embodiment 2：By CaF2, LiF (mol ratio CaF2:LiF=1:1) it is sufficiently mixed, in 870 DEG C of temperature, nitrogen ceiling
Melt under part, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, voltage 0.9V, current density 0.3A/cm2Under the conditions of it is pre-
It is electrolysed 0.7h；Then, the high pure nitrogen stirring melt of 3 times of fused salt volumes is passed through, then at vacuum 400Pa, 800 DEG C of temperature
1h is incubated, removes dross on surface of fusant.In the CaF of purification2- LiF media bases (mol ratio CaF2:LiF=1:1, quality percentage
Content is 96%) in melt, adds Yb2O3- NiO mixed powders (Yb2O3:NiO=1:4, mol ratio), lead to argon gas protection, temperature
920 DEG C, voltage 3.7V, current density 0.8A/cm2, negative electrode be metal Ni substrate, anode is high purity graphite, after electroplating time 3h
It is proposed that negative electrode is cooled to room temperature in argon gas.Nickel cathode surface after plating is after removing particle and burr processing, through 0.1mol/
L phosphoric acid cleaning, through 90 DEG C of drying 2h after then being cleaned with distilled water, after testing, 1.09mm can be formed in nickel metal surface
Ni-Yb alloy layers, significantly improve its surface comprehensive performance.
Embodiment 3：By CaF2, LiF (mol ratio CaF2:LiF=1:1) it is sufficiently mixed, in 880 DEG C of temperature, nitrogen ceiling
Melt under part, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, voltage 1.0V, current density 0.4A/cm2Under the conditions of it is pre-
It is electrolysed 0.8h；Then, the high pure nitrogen stirring melt of 4 times of fused salt volumes is passed through, then at vacuum 300Pa, 800 DEG C of temperature
1h is incubated, removes dross on surface of fusant.In the CaF of purification2- LiF media bases (mol ratio CaF2:LiF=1:1, quality percentage
Content is 96%) in melt, adds Yb2O3- NiO mixed powders (Yb2O3:NiO=1:4, mol ratio), lead to argon gas protection, temperature
940 DEG C, voltage 3.8V, current density 0.8A/cm2, negative electrode be metal Ni substrate, anode is high purity graphite, electroplating time 3.0h
It is proposed that negative electrode is cooled to room temperature in argon gas afterwards.Nickel cathode surface after plating is after removing particle and burr processing, warp
0.1mol/L phosphoric acid cleaning, through 90 DEG C of drying 2h after then being cleaned with distilled water, after testing, it can be formed in nickel metal surface
1.56mm Ni-Yb alloy layers, significantly improve its surface comprehensive performance.
Embodiment 4：By CaF2, LiF (mol ratio CaF2:LiF=1:1) it is sufficiently mixed, in 890 DEG C of temperature, nitrogen ceiling
Melt under part, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, voltage 1.1V, current density 0.5A/cm2Under the conditions of it is pre-
It is electrolysed 1h；Then, the high pure nitrogen stirring melt of 5 times of fused salt volumes is passed through, is then protected at vacuum 200Pa, 800 DEG C of temperature
Warm 1h, remove dross on surface of fusant.In the CaF of purification2- LiF media bases (mol ratio CaF2:LiF=1:1, quality percentage contains
Measure in 96%) melt, to add Yb2O3- NiO mixed powders (Yb2O3:NiO=1:4, mol ratio), lead to argon gas protection, temperature
950 DEG C, voltage 3.8V, current density 0.8A/cm2, negative electrode be metal Ni substrate, anode is high purity graphite, electroplating time 3.2h
It is proposed that negative electrode is cooled to room temperature in argon gas afterwards.Nickel cathode surface after plating is after removing particle and burr processing, warp
0.1mol/L phosphoric acid cleaning, through 90 DEG C of drying 2h after then being cleaned with distilled water, after testing, it can be formed in nickel metal surface
1.87mm Ni-Yb alloy layers, significantly improve its surface comprehensive performance.
Embodiment 5：By CaF2, LiF (mol ratio CaF2:LiF=1:1) it is sufficiently mixed, in 900 DEG C of temperature, nitrogen ceiling
Melt under part, using tungsten matter electrode as negative electrode, glassy carbon electrode is anode, voltage 1.2V, current density 0.6A/cm2Under the conditions of it is pre-
It is electrolysed 1h；Then, the high pure nitrogen stirring melt of 6 times of fused salt volumes is passed through, is then protected at vacuum 100Pa, 800 DEG C of temperature
Warm 1h, remove dross on surface of fusant.In the CaF of purification2- LiF media bases (mol ratio CaF2:LiF=1:1, quality percentage contains
Measure in 95%) melt, to add Yb2O3- NiO mixed powders (Yb2O3:NiO=1:4, mol ratio), lead to argon gas protection, temperature
950 DEG C, voltage 3.9V, current density 0.9A/cm2, negative electrode be metal Ni substrate, anode is high purity graphite, electroplating time 3.5h
It is proposed that negative electrode is cooled to room temperature in argon gas afterwards.Nickel cathode surface after plating is after removing particle and burr processing, warp
0.1mol/L phosphoric acid cleaning, through 90 DEG C of drying 2h after then being cleaned with distilled water, after testing, it can be formed in nickel metal surface
2.0mm Ni-Yb alloy layers, significantly improve its surface comprehensive performance.
Claims (2)
1. a kind of method of Electroplating from Molten Salts Ni-Yb alloy-layers modified metal nickel surface, it is characterized in that, comprise the following steps：
(1) raw material are matched：
With anhydrous CaF2, electrolyte based on LiF, Yb2O3, NiO be Ni-Yb alloy layers donor material；
Ratio requirement：
Anhydrous CaF2, LiF mixtures be system supporting electrolyte, account for Electroplating from Molten Salts system material mass percentage composition as 95~97%,
Remaining is Yb2O3And NiO, and CaF2:LiF mol ratio=1:1, Yb2O3:NiO mol ratio=1:4；
(2) anhydrous CaF2- LiF basic electrolytes purify：
By the anhydrous CaF in step (1)2, LiF be sufficiently mixed, melt under 850 DEG C~900 DEG C nitrogen protective conditions of temperature, with
Tungsten matter electrode is negative electrode, and glassy carbon electrode is anode, in 0.6~1.2V of voltage, 0.2~0.6A/cm of current density2Under the conditions of enter
Row preelectrolysis, time are 0.5~1h；Then, the high pure nitrogen stirring melt of 2~6 times of fused salt volumes is passed through, and in vacuum
1h is incubated at 100~500Pa, 800 DEG C of temperature, removes dross on surface of fusant；
(3) Molten Salt Electroplating：
To the CaF of step (2) purification2- LiF basic electrolytes melt lead to argon gas protection, 900~950 DEG C of temperature, voltage 3.5~
3.9V, 0.7~0.9A/cm of current density2Under the conditions of, taking-up negative electrode is cooled to room temperature in argon gas after electroplating 2.5~3.5h, cloudy
Extremely metal Ni substrate, anode are high purity graphite；
(4) it is surface-treated：
Nickel cathode surface after step (3) Molten Salt Electroplating is removed into particle and burr, and cleaned with 0.1mol/L phosphoric acid, then is used
Through 90 DEG C of drying 2h after distilled water cleaning.
2. a kind of method of Electroplating from Molten Salts Ni-Yb alloy-layers modified metal nickel surface according to claim 1, specific implementation
For：It is 1 by mol ratio:1 CaF2, LiF be sufficiently mixed, melt under 900 DEG C of temperature, nitrogen protective condition, with tungsten matter electrode
For negative electrode, glassy carbon electrode is anode, in voltage 1.2V, current density 0.6A/cm2Under the conditions of preelectrolysis 1h；Then, 6 are passed through
The high pure nitrogen stirring melt of times fused salt volume, 1h is then incubated at vacuum 100Pa, 800 DEG C of temperature, removes bath surface
Scum silica frost；The weight/mass percentage composition of purification be 95%, mol ratio 1:1 CaF2In-LiF media base melts, quality is added
Percentage composition is 5%, mol ratio 1:4 Yb2O3- NiO mixed powders, lead to argon gas protection, 950 DEG C of temperature, voltage 3.9V,
Current density 0.9A/cm2Under the conditions of, take out negative electrode after electroplating 3.5h and room temperature is cooled in argon gas, negative electrode is that metal is Ni-based
Body, anode are high purity graphite；Nickel cathode surface after plating is after removing particle and burr, the phosphoric acid cleaning through 0.1mol/L,
Through 90 DEG C of drying 2h after being cleaned again with distilled water；After testing, 2.0mm Ni-Yb alloy layers can be formed in nickel metal surface,
Significantly improve its surface comprehensive performance.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151805A (en) * | 2017-04-10 | 2017-09-12 | 中国科学院高能物理研究所 | Foam rare earth-nickel alloys and preparation method thereof, purposes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151805A (en) * | 2017-04-10 | 2017-09-12 | 中国科学院高能物理研究所 | Foam rare earth-nickel alloys and preparation method thereof, purposes |
Non-Patent Citations (3)
| Title |
|---|
| TAKAHISA IIDA ET AL.,: "Electrochemical formation of Yb /Ni alloy films by Li codeposition method in a molten LiCl/KCl/YbCl3 system", 《ELECTROCHIMICA ACTA》 * |
| TOSHIYUKI NOHIRA: "14 Electrochemical Formation", 《MOLTEN SALTS CHEMISTRY》 * |
| 赵桂芳: "熔盐电解法制取稀土金属的熔盐体系选择", 《江西有色金属》 * |
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