CN106987863A - The preparation technology of the bimodal nano-crystal nickel cobalt alloy of single pulse electrodpositing light two-phase - Google Patents
The preparation technology of the bimodal nano-crystal nickel cobalt alloy of single pulse electrodpositing light two-phase Download PDFInfo
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- CN106987863A CN106987863A CN201710152042.0A CN201710152042A CN106987863A CN 106987863 A CN106987863 A CN 106987863A CN 201710152042 A CN201710152042 A CN 201710152042A CN 106987863 A CN106987863 A CN 106987863A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/24—Alloys obtained by cathodic reduction of all their ions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- C—CHEMISTRY; METALLURGY
- 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
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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Abstract
The present invention relates to the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing.Comprise the concrete steps that：First by electroplate liquid through charcoal absorption removal of impurities and electrolysis removal of impurities before plating, the condition that preplating experiment determines the bimodal nickel-cobalt alloy plating of bright two-phase is then carried out in Hall slot device.It is stable between 2~5 in pH value, electroplated in the plating solution that concentration is 50~70g/L of nickel sulfate, 40~60g/L of nickel chloride, 40~50g/L of cobaltous sulfate is main salt, anode is used as using after soluble nickel plate surface treated, negative electrode is used as after stainless steel surface treated, using the coating of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing, wherein electrodeposition time is 2h~4h, and pulse current density is 2.5~3A/dm2, dutycycle is 20%~40%, and the cycle is 1~2ms, and mixing speed is 100~500r/min.Nickel-cobalt alloy plating surface-brightening made from this method, compact structure, it is careful to crystallize, and planarization is good, flawless, and with good decay resistance and higher intensity and plasticity.
Description
Technical field
The present invention relates to the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing, belong to plating and close
Golden collar domain.
Technical background
Nickel is a kind of silvery white non-ferrous metal, density 8.9,1455 DEG C of fusing point, 2915 DEG C of boiling point.Nickel has good machinery strong
Degree, ductility and corrosion resistance, are widely used in military industrial manufacturing enterprise, civilian industry, machinery manufacturing industry, petroleum industry etc.；Nickel cobalt
Alloy is a kind of permanent-magnet material, is widely used in the fields such as electronic telecontrol, atomic energy industry and ultrasonic technique.
Electrochemical deposition method is commonly called as plating, is a kind of in the plating solution containing coat of metal compound, with plated conduction
Part is negative electrode, by electrolysis, in piece surface to obtain firm binding force, coating is uniform, surface is careful
The method for electrochemical machining of metal film, while being also one of current quite extensive process for treating surface of application.According to its power supply
The species, its middle arteries such as conventional DC plating, alternating current-direct current superposition plating, pulse plating can be divided into by providing the mode difference of voltage x current
Punching plating is divided into pulse plating and double-pulse plating again.Monometallic plating is divided into according to the species of plating metallic element again and closed
Gold plating.
With science and technology and modern industry development the performance of functional material and structural material is proposed it is various
New demand, to the quality requirement of protective coating also more and more higher, the single metallic nickel plated layer of traditional plating due to:(1) plate
Layer poor (4) current efficiency of poor (3) the coating brightness of poor bonding strength (2) coating dispersibility is low, sedimentation rate is slow etc. because (5) are resistance to
Not high enough the factor of sour, alkaline-resisting, wearability can not fully meet some particular/special requirements.Thus, using a kind of metallic nickel as matrix,
Metallic nickel and metallic cobalt is co-deposited what is obtained by electro-deposition method, with its have higher hardness, heatproof, it is acidproof, alkaline-resisting,
Wearability, self lubricity, corrosion resistance, special decorative appearance and the nickel cobalt (alloy) plating for making electrical contact with the functions such as function, electro-catalysis
Layer extremely people pay close attention to.
Alloy plating should also possess following two key elements in addition to some primary conditions that must possess single metal deposition：
(1) in two kinds of metals of alloy plating, it is necessary at least to there is a kind of metal to go out from the aqueous solution deposition of its salt
Come.Especially it is emphasized that though some particulate metal such as tungsten, molybdenum can not come out from the aqueous solution deposition of its salt, it can be with
Iron family element is co-deposited, so the necessary condition of metal co-deposition, being not necessarily to each component can be individually from water
Deposition.
(2) two kinds of metal co-depositions must be fulfilled for their sedimentation potential want it is close can, if two kinds of metal current potential phases
If difference is very big, the meeting of metal current potential calibration is tried to be the first deposition, or even can repel the deposition precipitation of another metal below.
Pulse plating nickel cobalt (alloy) is compared with direct current electrode position nickel cobalt (alloy), and pulse plating nickel cobalt (alloy) has following side
The efficiency in face：
(1) densification, the sedimentary that conductance is high can be obtained；
(2) concentration polarization is reduced, cathode-current density is improved；
(3) it is reduced or eliminated that oxygen is crisp, improves the physical and mechanical property of coating；
(4) additive amount is reduced, the purity of coating is improved；
(5) porosity is reduced, the barrier propterty of coating is improved.
(6) pulse telegraph key can significantly improve the performance of coating, be that the development of electroplating technology opens new approach.
In a word, the heatproof of pulse electroplating bright biphase nanocrystalline nickel-cobalt alloy plating, it is acidproof, alkaline-resisting, wear-resisting, welding,
The performance indications such as toughness, plasticity, intensity, anti-corrosion, conductance, fastness, finish are increased substantially.Pulse electricity is utilized simultaneously
Deposition nickel cobalt (alloy) is avoided that the shortcoming of many traditional handicrafts.
The content of the invention
The technical problems to be solved by the invention are in view of the shortcomings of the prior art and provide a kind of single pulse electrodpositing light
The method of the bright bimodal nano-crystal nickel cobalt alloy of two-phase, nickel-cobalt alloy plating surface-brightening made from this method, compact structure is smooth
Property good, flawless, and with good decay resistance and higher intensity and plasticity.It is 66.7% (quality point in cobalt content
Number) when show the double structure containing face-centered cubic and Patterns for Close-Packed Hexagonal Crystal structure, while crystal grain is also presented special bimodal
Distribution is that CRYSTALLITE SIZES distribution is presented in crystal grain, i.e., same within sweep of the eye it is observed that big crystal grain and little crystal grain are (big brilliant
The size of grain can reach more than 100nm, and little crystallite size can reach tens nanometers).
In order to solve the above technical problems, the technical solution adopted by the present invention is：
The preparation technology of the bimodal nano-crystal nickel cobalt alloy of single pulse electrodpositing light two-phase, it is characterised in that：Including following
Processing step:First by electroplate liquid through charcoal absorption removal of impurities and electrolysis removal of impurities before plating, then enter again in Hall slot device
Row preplating experiment determines the addition scope of the additive of bright two-phase nickel-cobalt alloy plating, then with pH value it is stable 2~5 it
Between, electricity is carried out in the plating solution that concentration is 50~70g/L of nickel sulfate, 40~60g/L of nickel chloride, 40~50g/L of cobaltous sulfate is main salt
Plating, using after soluble nickel plate surface treated as anode, stainless steel is heavy using pulse electricity as negative electrode after surface treated
The bimodal nanocrystalline nickel-cobalt alloy plating of product technique electroplating bright two-phase, wherein electrodeposition time are 2h~4h, pulse current density
For 2.5~3A/dm2, dutycycle is 20%~40%, and the cycle is 1~2ms, and mixing speed is 100~500r/min.
According to such scheme, in described plating solution the also sodium sulphate including 20~30g/L as supporting electrolyte, 0.1~
0.5g/L saccharin, 0.01~0.05g/L Isosorbide-5-Nitrae-butynediols, 0.5g/L lauryl sodium sulfate.
By such scheme, each component and its content are in described plating solution：
The electroplate liquid preparation steps are as follows：
(1) quantitative nickel sulfate is weighed with assay balance, is added in beaker of the preprepared equipped with deionized water,
Dissolve by heating；
(2) weigh with assay balance quantitative nickel chloride respectively again and cobaltous sulfate is added separately to solution in step (1)
In, heating dissolves it.
The sustained-release acid for being used to adjust PH in described electroplate liquid is boric acid, and its process for preparation is as follows：
(1) clean beaker is added to quantitative deionized water；
(2) deionized water in step (1) is put on the heating furnace for be lined with asbestos gauge and boiled, then by quantifying for weighing up
Boric acid add in the deionized water boiled and be completely dissolved boric acid；
(3) boric acid all dissolved in step (2) is poured into rapidly in configured plating solution.
Also the anionic surfactant so lauryl sulfate including 0.5-0.6g/L is used as profit in described plating solution
Humectant, the process for preparation of wetting agent used is as follows：
(1) first a certain amount of lauryl sodium sulfate is weighed with assay balance to be placed in clean beaker；
(2) then add minimal amount of deionized water the lauryl sodium sulfate in step (1) is tuned into starchiness；
(3) deionized water boiled with electrothermal furnace is finally poured into the beaker equipped with starchy lauryl sodium sulfate
In, boiling 30min makes it fully dissolve, finally in configured plating solution is poured into.
The plating solution will carry out adsorption-edulcoration before plating, and the granular active carbon that 3g/L is weighed with assay balance is added to
In the plating solution of the preparation, then the stirring and adsorbing 1h under magneton stirring action takes out granular activated carbon, finally by true
Empty suction filtration removes the powdered activated carbon of residual in the plating solution；
The plating solution will also carry out electrolysis removal of impurities after charcoal absorption removal of impurities, and the condition of electrolysis removal of impurities is low current
It is usually 0.1A, electrolysis time is 6h, anode or the soluble nickel plate that purity is more than 99.99%, and negative electrode is to be converted into ripple
The thin steel plate of line shape.
By Hull cell carry out preplating experiment determine electroplating bright nickel cobalt (alloy) condition, Hull cell preplating experiment include with
Lower step：
Step one：250ml examination plating solution is measured with graduated cylinder, saccharin and Isosorbide-5-Nitrae-butynediols is not added with, pH value is regulated stable
Between 2~5；
Step 2：Plating solution therein is heated to 45~65 DEG C by the heating rod in Hull cell；
Step 3：The specific copper sheet for Hull cell test that surface is cleaned by processing is put into Hull cell；
Step 4：Start examination plating, examination plating electric current be direct current and it is constant be 1A, examination plating during enter manually by using glass bar
Row stirring, the size that PH is adjusted at any time is stabilized it in the scope required by step one, tries plating time 10min；
Step 5：Dried up after the copper sheet for trying to have plated is cleaned, visually observe whether its surface has the bright area of larger area
Domain；The situation that copper sheet surrounding is tilted is observed on the desktop for being then placed on surfacing and being laid flat, so as to judge to answer in coating
The size of power；
Step 6：If the copper sheet surface-brightening region that examination has been plated is less and there is the situation of tilting at four angles, it need to measure again
250ml plating solution is taken, then the consumption of saccharin and Isosorbide-5-Nitrae-butynediols is constantly changing on the basis of upper one examination plating piece, so that
Determine the condition of the addition of bright coating additive.
Plating solution process is stirred by electric stirring oar, so that the composition uniformity at each position of plating solution.
The purity of the soluble nickel plate of described anode is more than 99.99%, and the electrode spacing of the anode and negative electrode is
15~20cm, specification is the ㎝ of the ㎝ of 10 ㎝ × 10 × 0.2, and the area ratio of anode and negative electrode is more than or equal to 4:1.
Negative electrode stainless steel sequentially passes through 120 mesh, 220 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1500 mesh, 2000 mesh,
The abrasive paper for metallograph of 3000 mesh is polishing to mirror effect, puts it into 8~10min of ultrasound in 80 DEG C of alkali wash waters and carries out decontamination oil removing
Processing, is then put into ultrasonically treated 2min in 80 DEG C of deionized water by the matrix that oil removal treatment is crossed, and removing remains in stainless
The alkali wash water on steel matrix surface, is finally put into 30~60s of ultrasonic vibration in dilution heat of sulfuric acid by matrix and is derusted and surface work
Change is handled.
Beneficial effects of the present invention：
1. there is preferable adsorption capacity to adsorb some impurity in plating solution to purify using porous activated carbon by the present invention
Plating solution.
2. an electroplating technology at low currents, plating is further removed by being electrolysed removal of impurities after activated carbon removal of impurities
Impurity in liquid so that plating solution is more pure, so as to ensure the purity and profile pattern of alloy layer.
3. an electroplating technology is before real plating, first carry out Hull cell test to determine electroplating bright nickel cobalt (alloy) coating
Additive addition scope, so as to ensure the brightness of alloy layer.
4. the acid used in an electroplating technology pickling is the dilute sulfuric acid that volume fraction is 10%, it is to avoid with watery hydrochloric acid to environment
The pollution brought.
5. an electroplating technology all uses ultrasonic vibration during alkali cleaning, washing, pickling this three steps of washing, to make washing
Effect is more preferable.
6. this electroplating technology coating is bright, composition is uniform, with higher intensity hardness and plasticity, acid-fast alkali-proof and resistance to
Mill performance there has also been larger raising.The double structure for having FCC and HCP concurrently, and size are relatively especially presented in microstructure
The two peak structure of crystal grain distribution.
Brief description of the drawings
Fig. 1 schemes for the TEM of the bimodal nickel-cobalt alloy plating of single pulse electrodpositing
Fig. 2 is the TEM figures for the nanocrystalline nickel-cobalt alloy plating that cobalt content is 50%
Fig. 3 is the TEM figures for the nanocrystalline nickel-cobalt alloy plating that cobalt content is 70%
Fig. 4 is the energy spectrum diagram for the nanocrystalline nickel-cobalt alloy plating that cobalt content is 50%
Fig. 5 is the energy spectrum diagram for the nanocrystalline nickel-cobalt alloy plating that cobalt content is 70%
Fig. 6 is the XRD of the nanocrystalline nickel-cobalt alloy plating of different cobalt contents
Embodiment
Embodiment 1
A kind of preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing, comprises the following steps：
A. the preparation of plating solution：Added in nickel sulfate 60g/L, nickel chloride 50g/L, cobaltous sulfate 45g/L is the plating solutions of main salt
50g/L boric acid, adds deionized water by plating solution trim to 5L (4L is used to formally electroplate, and 1L is used to try plating experiment).
B. adsorption-edulcoration：It will prepare and add 3g/L activated carbon without additivated plating solution and be put into magneton, in room
The lower stirring and adsorbing 1h of temperature.The activated carbon remained in plating solution is got rid of finally by suction filtration.
C. it is electrolysed removal of impurities：The complete plating solution of suction filtration is carried out into electrolysis absorption in the case where average current is the 0.1A pulse power to remove
It is miscellaneous, it is electrolysed 6h.
D. preplating is tested：
Step one：250ml plating solution is measured from the 5L plating solutions being electrolysed, 0.5g/L dodecyl sulphate is only added
Sodium, is not added with saccharin and Isosorbide-5-Nitrae-butynediols.The temperature of the plating solution in Hull cell is heated to 55 DEG C by heating rod and remains permanent
It is fixed.
Step 2：In dc source and electric current is constant in the case of 1A, preplating is carried out.PH value is steady during plating is tried
3.8 are scheduled on, and constantly plating solution is stirred, plating time 10min is tried.
Step 3：Plating piece is rinsed well with deionized water, then dried up.
Step 4：By on the plating piece of drying is placed on surfacing and is laid flat desk, the angle that observation copper sheet corner is tilted
Size.The brightness on copper sheet surface is observed simultaneously.
Step 5：If above-mentioned plating piece corner has larger tilting or plating piece surface not bright enough.Again measure 250ml's
Plating solution is constantly changing saccharin on the basis of the plating solution of step one and the consumption of 1,4- butynediols obtains adding for bright coating
Plus the amount ranges of agent.
E. part is washed：In the alkali wash water that matrix stainless steel is put into 80 DEG C, surpass in supersonic frequency is 30kHz ultrasonic machine
Sound 10min, is then placed in into 80 DEG C of deionized water the alkali that ultrasonic vibration 2min (f=30kHz) removes matrix surface residual
Washing lotion.Matrix is finally put into the dilute sulfuric acid of volume fraction 10% ultrasonic pickling 30s.
F. formal plating：The consumption for the additive that the preplating stage is determined is added in 4L plating solution, while will be treated
Matrix, which is put into 4L plating solution, starts plating.Plating conditions are：Pulse is electroplated, average current 0.4A, ton=0.2ms, toff=
0.8ms, dutycycle 20%, electroplating time 2h, thickness 25um, bath temperature is stable at 55 DEG C, and pH value is stable 3.8.
G. plating posttreatment：After the part plated is washed down with deionized water, drying obtains testpieces.
Embodiment 2
A kind of preparation technology of the bright biphase nanocrystalline nickel cobalt (alloy) of single pulse electrodpositing, comprises the following steps：
A. the preparation of plating solution：Added in nickel sulfate 50g/L, nickel chloride 40g/L, cobaltous sulfate 40g/L is the plating solutions of main salt
40g/L boric acid, adds deionized water by plating solution trim to 5L (4L is used to formally electroplate, and 1L is used to try plating experiment).
B. adsorption-edulcoration：It will prepare and add 3g/L activated carbon without additivated plating solution and be put into magneton, in room
The lower stirring and adsorbing 1h of temperature.The activated carbon remained in plating solution is got rid of finally by suction filtration.
C. it is electrolysed removal of impurities：The complete plating solution of suction filtration is carried out into electrolysis absorption in the case where average current is the 0.1A pulse power to remove
It is miscellaneous, it is electrolysed 6h.
D. preplating is tested：
Step one：250ml plating solution is measured from the 5L plating solutions being electrolysed, 0.5g/L dodecyl sulphate is only added
Sodium, is not added with saccharin and Isosorbide-5-Nitrae-butynediols.The temperature of the plating solution in Hull cell is heated to 45 DEG C by heating rod and remains permanent
It is fixed.
Step 2：In dc source and electric current is constant in the case of 1A, preplating is carried out.PH value is steady during plating is tried
4.5 are scheduled on, and constantly plating solution is stirred, plating time 10min is tried.
Step 3：Plating piece is rinsed well with deionized water, then dried up.
Step 4：By on the plating piece of drying is placed on surfacing and is laid flat desk, the angle that observation copper sheet corner is tilted
Size.The brightness on copper sheet surface is observed simultaneously.
Step 5：If above-mentioned plating piece corner has larger tilting or plating piece surface not bright enough.Again measure 250ml's
Plating solution is constantly changing saccharin on the basis of the plating solution of step one and the consumption of 1,4- butynediols obtains adding for bright coating
Plus the amount ranges of agent.
E. part is washed：In the alkali wash water that matrix stainless steel is put into 60 DEG C, surpass in supersonic frequency is 35kHz ultrasonic machine
Sound 8min, is then placed in into 60 DEG C of deionized water the alkali cleaning that ultrasonic vibration 2min (f=30kHz) removes matrix surface residual
Liquid.Matrix is finally put into the dilute sulfuric acid of volume fraction 10% ultrasonic pickling 45s.
F. formal plating：The consumption for the additive that the preplating stage is determined is added in 4L plating solution, while will be treated
Matrix, which is put into 4L plating solution, starts plating.Plating conditions are：Pulse is electroplated, average current 0.6A, ton=0.8ms, toff=
1.2ms, dutycycle 40%, electroplating time 3h, thickness 35um, bath temperature is stable at 45 DEG C, and pH value is stable 4.5.
G. plating posttreatment：After the part plated is washed down with deionized water, drying obtains testpieces.
Embodiment 3
A kind of preparation technology of the bright biphase nanocrystalline nickel cobalt (alloy) of single pulse electrodpositing, comprises the following steps：
A. the preparation of plating solution：Added in nickel sulfate 70g/L, nickel chloride 60g/L, cobaltous sulfate 50g/L is the plating solutions of main salt
45g/L boric acid, adds deionized water by plating solution trim to 5L (4L is used to formally electroplate, and 1L is used to try plating experiment).
B. adsorption-edulcoration：It will prepare and add 3g/L activated carbon without additivated plating solution and be put into magneton, in room
The lower stirring and adsorbing 1h of temperature.The activated carbon remained in plating solution is got rid of finally by suction filtration.
C. it is electrolysed removal of impurities：The complete plating solution of suction filtration is carried out into electrolysis absorption in the case where average current is the 0.1A pulse power to remove
It is miscellaneous, it is electrolysed 6h.
D. preplating is tested：
Step one：250ml plating solution is measured from the 5L plating solutions being electrolysed, 0.5g/L dodecyl sulphate is only added
Sodium, is not added with saccharin and Isosorbide-5-Nitrae-butynediols.The temperature of the plating solution in Hull cell is heated to 65 DEG C by heating rod and remains permanent
It is fixed.
Step 2：In dc source and electric current is constant in the case of 1A, preplating is carried out.PH value is steady during plating is tried
5 are scheduled on, and constantly plating solution is stirred, plating time 10min is tried.
Step 3：Plating piece is rinsed well with deionized water, then dried up.
Step 4：By on the plating piece of drying is placed on surfacing and is laid flat desk, the angle that observation copper sheet corner is tilted
Size.The brightness on copper sheet surface is observed simultaneously.
Step 5：If above-mentioned plating piece corner has larger tilting or plating piece surface not bright enough.Again measure 250ml's
Plating solution is constantly changing saccharin on the basis of the plating solution of step one and the consumption of 1,4- butynediols obtains adding for bright coating
Plus the amount ranges of agent.
E. part is washed：In the alkali wash water that matrix stainless steel is put into 40 DEG C, surpass in supersonic frequency is 40kHz ultrasonic machine
Sound 6min, is then placed in into 40 DEG C of deionized water the alkali cleaning that ultrasonic vibration 2min (f=30kHz) removes matrix surface residual
Liquid.Matrix is finally put into the dilute sulfuric acid of volume fraction 10% ultrasonic pickling 60s.
F. formal plating：The consumption for the additive that the preplating stage is determined is added in 4L plating solution, while will be treated
Matrix, which is put into 4L plating solution, starts plating.Plating conditions are：Pulse is electroplated, average current 0.4A, ton=0.2ms, toff=
0.8ms, dutycycle 20%, electroplating time 4h, thickness 40um, bath temperature is stable at 65 DEG C, and pH value is stable 5.
G. plating posttreatment：After the part plated is washed down with deionized water, drying obtains testpieces.
Claims (10)
1. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of single pulse electrodpositing light two-phase, it is characterised in that including following work
Skill step：First by electroplate liquid through charcoal absorption removal of impurities and electrolysis removal of impurities before plating, then carried out again in Hall slot device
Preplating experiment determines the condition of bright biphase nanocrystalline nickel-cobalt alloy plating, then in stable between 2~5, the concentration with pH value
To be electroplated in 50~70g/L of nickel sulfate, 40~60g/L of nickel chloride, the plating solution that 40~50g/L of cobaltous sulfate is main salt, with can
As anode after dissolubility nickel plate surface treated, as negative electrode after stainless steel surface treated, using single pulse electrodpositing technique
The bimodal nickel-cobalt alloy plating of electroplating bright Nanocrystalline Two-phase, wherein electrodeposition time be 2h~4h, pulse current density be 2.5~
3A/dm2, dutycycle be 20%~40%, the cycle be 1~2ms, electrodeposition temperature be 45~65 DEG C, mixing speed be 100~
500r/min。
2. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1, its
It is characterised by：The also sodium sulphate including 20~30g/L is as supporting electrolyte in the plating solution, and 0.1~0.5g/L saccharin is made
For primary brightener, 0.01~0.05g/L Isosorbide-5-Nitrae-butynediols is used as second-class brightener.
3. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1 or 2,
It is characterized in that：The electroplate liquid preparation steps are as follows：
(1) quantitative nickel sulfate is weighed with assay balance, is added in beaker of the preprepared equipped with deionized water, heating
Dissolving；
(2) weigh with assay balance quantitative nickel chloride respectively again and cobaltous sulfate is added separately in the solution in step (1), plus
Heat dissolves it.
4. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 3, its
It is characterised by：The sustained-release acid for being used to adjust PH in described electroplate liquid is boric acid, and its process for preparation is as follows：
(1) clean beaker is added to quantitative deionized water；
(2) deionized water in step (1) is put on the heating furnace for be lined with asbestos gauge and boiled, then by the quantitative boron weighed up
Acid, which is added in the deionized water boiled, is completely dissolved boric acid；
(3) boric acid all dissolved in step (2) is poured into rapidly in configured plating solution.
5. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 3, its
It is characterised by：Also the anionic surfactant so lauryl sulfate including 0.5-0.6g/L is used as profit in described plating solution
Humectant, the process for preparation of wetting agent used is as follows：
(1) first a certain amount of lauryl sodium sulfate is weighed with assay balance to be placed in clean beaker；
(2) then add minimal amount of deionized water the lauryl sodium sulfate in step (1) is tuned into starchiness；
(3) finally the deionized water boiled with electrothermal furnace is poured into the beaker equipped with starchy lauryl sodium sulfate, boiled
30min makes it fully dissolve, finally in configured plating solution is poured into.
6. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 3, its
It is characterised by：The plating solution will carry out adsorption-edulcoration before plating, and the granular active carbon that 3g/L is weighed with assay balance is added
Into the plating solution of the preparation, then the stirring and adsorbing 1h under magneton stirring action takes out granular activated carbon, finally by
Vacuum filtration removes the powdered activated carbon of residual in the plating solution；
The plating solution will also carry out electrolysis removal of impurities after charcoal absorption removal of impurities, and the condition of electrolysis removal of impurities is that low current is to lead to
It is often 0.1A, electrolysis time is 6h, anode or the soluble nickel plate that purity is more than 99.99%, and negative electrode is to be converted into corrugated
Thin steel plate.
7. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1, its
It is characterised by：The condition that preplating experiment determines electroplating bright nickel cobalt (alloy) is carried out by Hull cell, Hull cell preplating experiment is included
Following steps：
Step one：250ml examination plating solution is measured with graduated cylinder, saccharin and Isosorbide-5-Nitrae-butynediols is not added with, regulate pH value it is stable 2~
Between 5；
Step 2：Plating solution therein is heated to 45~65 DEG C by the heating rod in Hull cell；
Step 3：The specific copper sheet for Hull cell test that surface is cleaned by processing is put into Hull cell；
Step 4：Start examination plating, examination plating electric current be direct current and it is constant be 1A, examination plating during stirred manually by using glass bar
Mix, the size that PH is adjusted at any time is stabilized it in the scope required by step one, try plating time 10min；
Step 5：Dried up after the copper sheet for trying to have plated is cleaned, visually observe whether its surface has the lighted region of larger area；So
The situation that copper sheet surrounding is tilted is observed on the desktop for placing it in surfacing afterwards and being laid flat, so as to judge the big of stress in coating
It is small；
Step 6：If the copper sheet surface-brightening region that examination has been plated is less and there is the situation of tilting at four angles, it need to measure again
250ml plating solution, then try at upper one to be constantly changing the consumption of saccharin and Isosorbide-5-Nitrae-butynediols on the basis of plating piece, so that really
Determine the condition of the addition of bright coating additive.
8. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1, its
It is characterised by：Plating solution process is stirred by electric stirring oar, so that the composition uniformity at each position of plating solution.
9. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1, its
It is characterised by：The purity of the soluble nickel plate of described anode is more than 99.99%, and the electrode spacing of the anode and negative electrode is
15~20cm, specification is the ㎝ of the ㎝ of 10 ㎝ × 10 × 0.2, and the area ratio of anode and negative electrode is more than or equal to 4:1.
10. the preparation technology of the bimodal nano-crystal nickel cobalt alloy of the bright two-phase of single pulse electrodpositing according to claim 1, its
It is characterised by：Negative electrode stainless steel sequentially passes through 120 mesh, 220 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1500 mesh, 2000
Mesh, the abrasive paper for metallograph of 3000 mesh is polishing to mirror effect, puts it into 8~10min of ultrasound in 80 DEG C of alkali wash waters and is decontaminated
Oil removal treatment, is then put into ultrasonically treated 2min in 80 DEG C of deionized water by the matrix that oil removal treatment is crossed, and removing is remained in
The alkali wash water on stainless steel base surface, is finally put into 30~60s of ultrasonic vibration in dilution heat of sulfuric acid by matrix and is derusted and table
Face activation process.
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| CN112831810B (en) * | 2020-12-31 | 2023-05-30 | 大连大学 | Process for preparing micro-columnar structure by maskless localized electrodeposition method |
| CN113174607A (en) * | 2021-04-29 | 2021-07-27 | 韩山师范学院 | Electrochemical preparation method of porous Ni-Co/graphene electrode |
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| CN114717573A (en) * | 2022-04-13 | 2022-07-08 | 华南理工大学 | Cobalt-based metal/metal oxide hydrogen evolution catalyst with heterogeneous phase, and preparation and application thereof |
| CN114717573B (en) * | 2022-04-13 | 2023-06-16 | 华南理工大学 | Cobalt-based metal/metal oxide hydrogen evolution catalyst with heterogeneous junction and preparation and application thereof |
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