CN107604397A - The electro-plating method of continuous casting crystallizer copper plate deposit N i Co B alloy layers - Google Patents
The electro-plating method of continuous casting crystallizer copper plate deposit N i Co B alloy layers Download PDFInfo
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Abstract
The invention discloses a kind of electroplate liquid of continuous casting crystallizer copper plate deposit N i Co B alloy layers, belong to electroplating technology, the electroplate liquid, in terms of mass concentration, composition includes：170 ~ 350g/L of nickel salt, 5 ~ 50g/L of cobalt salt, 0.5 ~ 4g/L of sodium borohydride, 20 ~ 60g/L of ethylenediamine, 30 ~ 50g/L of buffer.The Ni Co B alloy layers that electroplate liquid of the present invention is prepared have a good covering power, and microhardness is superior up to 1000HV, corrosion resisting property.
Description
Technical field
The invention belongs to electroplating technology, and in particular to continuous casting crystallizer copper plate deposit N i-Co-B alloy layers
Electro-plating method.
Background technology
Conticaster is the key equipment of steel-making, and crystallizer is the core component of conticaster, and its quality directly influences
The quality of strand and the operating rate of conticaster.It is cold that the molten steel of boiling and the protection slag liquid of melting directly contact crystallizer copper plate surface
But into strand, and have along with the sliding friction between inwall and strand, severe operating environment requirements crystallizer copper plate surface
More preferable thermal conductivity, higher mechanical strength, the wearability and corrosion resisting property having had.In steelmaking process, molten steel is not
Disconnectedly by crystallizer, pulled straight after being condensed into hard green shell below crystallizer, realize continuous production.With steel and iron industry
Rapid development, higher and higher requirement is proposed to the performance of crystallizer material surface, the development of crystallizer will continue towards
Direction with high mechanical properties, good thermal conductivity, wearability and decay resistance is developed.
Currently, in copper plate of crystallizer working face treatment technology, mainly there are nickel plating, nickel cobalt (alloy), dilval, the conjunction of cobalt nickel
Gold and hot-spraying coating etc., however, the relatively low 200HV of nickel coating hardness, wearability is poor, influences crystallizer life-span, electronickelling
Cobalt alloy, though crystallizer service life is improved, but still present situation can not be met；Ferro-nickel alloy electroplating, wearability is higher but fragility
Greatly, washed away in casting process by molten steel and be also easy to produce crackle；Cobalt-nickel alloy is electroplated, cobalt cost is too high, though improve the resistance to of alloy-layer
Mill property, but alloy-layer fragility, internal stress are larger, and alternating thermal stress resisting is poor, causes copper plate of crystallizer improper offline.
Publication No. CN102352522A patent discloses electro-deposition preparation side of the Ni-Co-B alloys for hard chromium
Method, it is related to preparation method of the Ni-Co-B alloys for hard chromium, method 1：Take nickel salt, cobalt salt, nickel chloride, boric acid, amine boronation
The quick high leveling nickel plating polishing material A agent of compound, NI3# and lauryl sodium sulfate；Configure alloy electroplating bath；Plating piece is laggard through handling
Row plating, method 2：Take the quick high leveling nickel plating polishing material A agent and 12 of nickel chloride, cobalt salt, boric acid, amine boron compound, NI3#
Sodium alkyl sulfate；Configure alloy electroplating bath；Plating piece is electroplated after processing.The invention is obtained with the deposition velocity higher than 60 μm/h
It is bright uniformly, hardness be 770 ~ 800HV50, corrosion resistance and the good Ni-Co-B alloy layers of adhesion, negative electrode in electroplating process
Current efficiency is higher than 96%, and coating hardness after being heat-treated 1 ~ 3h at 150 ~ 400 DEG C can be improved to 1055 ~ 1108HV50.The hair
It is bright following deficiency to be present：The not thermally treated hardness of Ni-Co-B alloy layers is up to 800HV, needs further to be improved, and
Used amine boron compound, reproducibility is weaker, and reduction efficiency is relatively low, and B content is relatively low in obtained Ni-Co-B alloy layers,
Therefore relatively thin nickel cobalt boron coating is preferably only prepared, the wear-resisting of coating, decay resistance are poor.
Publication No. CN103820828A discloses a kind of Ni nanoparticle-Co-B Alloy Platings of continuous casting crystallizer copper plate/copper pipe
Layer process, through polishing, oil removing, wash, be loaded, deionized water, activation, plating, washing, there is higher hardness and anticorrosive energy
Power, plating deposition rate is fast, and tint is bright, bright-coloured, smoothly, in mirror-like, without crackle.In addition, the solution of the invention
Depth capability and covering power it is stronger, its chromium plating compared to depth capability be traditional 17.5 times, covering power is 3.2 times.
And it is smaller with environmental pollution, waste water, waste liquid, waste gas treatment process are simple.Following deficiency be present in the invention：The invention
The electroplating bath components complexity of Ni-Co-B alloy layers is prepared, the hardness of Ni-Co-B alloy layers is relatively low, hard after Overheating Treatment
Degree also only has 900HV, it is impossible to meets existing continuous casting demand well.
The content of the invention
In view of this, it is an object of the invention to provide a kind of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers
Electroplate liquid and its electro-plating method, the Ni-Co-B alloy layers being prepared using the electroplate liquid have good covering power, show
Microhardness is superior up to 1000HV, corrosion resisting property.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, in terms of mass concentration, composition includes：Nickel
170 ~ 350g/L of salt, 5 ~ 50g/L of cobalt salt, 0.5 ~ 4g/L of sodium borohydride, 20 ~ 60g/L of ethylenediamine, 30 ~ 50g/L of buffer.
Preferably, the nickel salt is the composition of nickel sulfate and nickel chloride, wherein：150 ~ 300g/L of nickel sulfate, nickel chloride
20~50g/L。
Preferably, the cobalt salt is cobaltous sulfate.
Preferably, the buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
Preferably, the electroplate liquid composition, in addition to：0.01 ~ 0.1g/L of surfactant.
Preferably, the pH value of the electroplate liquid is 9 ~ 14.
Preferably, the electro-plating method of the electroplate liquid of the continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, be by
Copper plate base body by pretreatment is placed in the electroplate liquid, using pulse plating, using the copper plate base body as negative electrode, with nickel
Pearl carries out negative electrode plating as anode.
Preferably, the make-to-break ratio of the pulse plating is 1：6, average current density is 1 ~ 4 A/dm2。
Preferably, the temperature of the pulse plating is 55 ~ 70 DEG C.
Preferably, the composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：50% ~ 69%Ni, 30% ~ 45%
Co and 1% ~ 5%B.
Compared with prior art, beneficial effects of the present invention are as follows：
The present invention is directed to the problems such as low current copper plate of crystallizer steel transportation amount, serious wear, short service life, it is proposed that a kind of continuous casting
The electroplate liquid and its electro-plating method of copper plate of crystallizer deposit N i-Co-B alloy layers, the Ni-Co-B alloys being thus prepared
The covering power of coating copper plate of crystallizer is strong, microhardness significantly improves up to 1000HV, corrosion resisting property.1. when sodium borohydride adds
When entering amount in 0.63/L ~ 2.29/L this segment limit, plating speed is improved with the addition of sodium borohydride and almost linearly increased；Work as boron
When sodium hydride addition is in the range of 2.29/L ~ 4.29/L, plating speed slightly reduces with the increase of potassium borohydride, works as sodium borohydride
After addition further improves, plating speed declines rapidly therewith increasing.The fast this variation tendency with sodium borohydride addition of plating
Show：When the concentration of reducing agent in plating solution is relatively low, the reducing power of plating solution can be strengthened by increasing the addition of reducing agent,
Greatly improve plating speed；After the reducing power of plating solution strengthens to a certain extent, it is no longer just the major control of plating solution reaction
Factor, the increase of reductant concentration not only can not further improve plating speed, and continue to increase reductant concentration and can accelerate plating solution
Decompose, cause plating speed is rapid to decline.Therefore the dosage selection of sodium borohydride of the present invention is 0.5 ~ 4g/L.2. buffer is in the present invention
In effect be that can supplement the hydrogen ion consumed by the precipitation of cathodic hydrogen, maintain the pH value of electroplate liquid relatively stable, from
And the current efficiency of negative electrode is improved, improve the surface quality of coating；The ductility and coating and copper coin of coating can also be improved simultaneously
The adhesion of base material.Determine the application buffer using sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1 by long-term practice：1
The mixture of composition, content range are 30 ~ 50g/L, and the normal operation of electroplating activity is may insure in this concentration range, and
To improving coating surface quality, improving coating performance etc. has obvious action.
Each composition collaborative combination of the present invention so that gained Ni-Co-B alloy layer superior performances, electroplate liquid have good
Covering power, electroplating evenness more than 92%, chemical property is good, stability is high, microhardness up to 1000 HV, and Ni-Co-
B alloy layer compact structures, it is high with matrix material combination force intensity, have high rigidity, high corrosion-resistant and high-wearing feature etc. excellent
Performance, the service life of continuous casting crystallizer copper plate is set to extend more than 2 times.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
A kind of electro-plating method of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, comprises the following steps：
Step S1, pre-process：Pre-treatment before plating is carried out to copper plate base body, included successively：Cleaning is deoiled, mechanical sandblasting plucking, electricity
Degreasing, ultrasonic degreasing are solved, negative electrode fixes plating profiling fixture and acid solution activation process, obtains copper plate base body to be plated；
Step S2, electroplate：Electroplate liquid is injected in electroplating bath, adjusts the pH of the electroplate liquid, electroplate liquid is heated, rises to temperature
Setting value, then copper plate base body to be plated is put into electroplating bath as negative electrode, anode is put into electroplating bath, switch on power beginning
Plating, the thickness to nickel cobalt boron alloy cladding reach setting value, terminate plating, produce the crystallizer of electronickelling cobalt-boron alloy coating
Copper coin.
The copper plate of crystallizer of electronickelling cobalt-boron alloy coating obtained by the present invention is subjected to vacuum heat, vacuum≤
10-2In Pa application of vacuum stove, temperature is 300 ~ 400 DEG C and kept for 2 ~ 3 hours.
After Overheating Treatment, the microhardness of copper plate of crystallizer can improve more than 1.6 times.
The thickness of nickel cobalt boron alloy cladding of the present invention is 0.5 ~ 5mm.
The electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers of the present invention, in terms of mass concentration, composition bag
Include：170 ~ 350g/L of nickel salt, 5 ~ 50g/L of cobalt salt, 0.5 ~ 4g/L of sodium borohydride, 20 ~ 60g/L of ethylenediamine, 30 ~ 50g/L of buffer.
As a preference of the present invention, the nickel salt is the composition of nickel sulfate and nickel chloride, wherein：Nickel sulfate 150 ~
300g/L, 20 ~ 50g/L of nickel chloride.
As a preference of the present invention, the cobalt salt is cobaltous sulfate.
As a preference of the present invention, the buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：1 composition mixes
Compound.
As a preference of the present invention, the electroplate liquid composition also includes：The g/L of surfactant 0.01 ~ 0.1, the surface
Activating agent is preferably wetting agent MT-80.
As a preference of the present invention, the pH value of the electroplate liquid is 9 ~ 14.Adjusted using sulfamic acid and sodium hydroxide
Section.
The electro-plating method of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers of the present invention, it is by by pre- place
The copper plate base body of reason is placed in the electroplate liquid, and using pulse plating, using the copper plate base body as negative electrode, sun is used as using nickel bead
Pole, carry out negative electrode plating.
As a preference of the present invention, the make-to-break ratio of the pulse plating is 1：6, average current density is 1 ~ 4 A/dm2。
As a preference of the present invention, the temperature of the pulse plating is 55 ~ 70 DEG C.
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：50% ~ 69%Ni, 30% ~ 45%Co and 1% ~
5%B。
In the present invention, coating deposition rate is 20 μm/h, and under the deposition velocity, obtained coating surface crystal grain is careful,
And particulate is tightly combined, surface impunctate occurs.
The part preferred embodiment of the present invention is set forth below.In following embodiments of the present invention, continuous casting crystallizer copper plate electricity
It is identical to deposit the electro-plating method basic step of Ni-Co-B alloy layers, only difference is described in detail.
Embodiment 1
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, is comprised the following steps that：
Step S1, pre-process：Pre-treatment before plating is carried out to copper plate base body, included successively：Cleaning is deoiled, mechanical sandblasting plucking, electricity
Degreasing, ultrasonic degreasing, negative electrode fixation plating profiling fixture and acid solution activation process are solved, obtains copper plate base body to be plated；
Step S2, electroplate：Electroplate liquid is injected in electroplating bath, adjusts the pH of the electroplate liquid, electroplate liquid is heated, rises to temperature
Setting value, then copper plate base body to be plated is put into electroplating bath as negative electrode, anode is put into electroplating bath, switch on power progress
Pulse plating, the thickness to nickel cobalt boron alloy cladding reach setting value, terminate plating, produce the knot of electronickelling cobalt-boron alloy coating
Brilliant device copper coin.
In the present embodiment, the composition of electroplate liquid, in terms of mass concentration, it is：Nickel sulfate 220g/L, nickel chloride 35g/L, sulfuric acid
Cobalt 30g/L, sodium borohydride 2.5g/L, ethylenediamine 40g/L, buffer 40g/L.
The buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
The pH value of the electroplate liquid is 10.5, and temperature is 60 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density 2.5A/
dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：60.2%Ni, 37.3%Co and 2.5%B.
Embodiment 2
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid is：Nickel sulfate 150g/L, nickel chloride 20g/L, cobaltous sulfate 50g/L, sodium borohydride 4g/L, ethylenediamine
45/L, buffer 35g/L.
The pH value of the electroplate liquid is 9, and temperature is 55 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density is 2 A/
dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：49.8%Ni, 45.2%Co and 5%B.
Embodiment 3
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid is：Nickel sulfate 300g/L, nickel chloride 50g/L, cobaltous sulfate 5g/L, sodium borohydride 0.5g/L, ethylenediamine
35g/L, buffer 45g/L.
The pH value of the electroplate liquid is 14, and temperature is 70 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density 3A/dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：68..3%Ni, 30.7%Co and 1%B.
Embodiment 4
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid is：Nickel sulfate 180g/L, nickel chloride 25g/L, cobaltous sulfate 15g/L, sodium borohydride 1.0g/L, ethylenediamine
20g/L, buffer 30g/L.
The pH value of the electroplate liquid is 10, and temperature is 58 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density 1.2A/
dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：54.6%Ni, 44%Co and 1.6%B.
Embodiment 5
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid is：Nickel sulfate 250g/L, nickel chloride 40g/L, cobaltous sulfate 38g/L, sodium borohydride 3.0g/L, ethylenediamine
50g/L, buffer 42g/L.
The pH value of the electroplate liquid is 10.8, and temperature is 60 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density is 2.5 A/
dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：60.4%Ni, 38.3%Co and 1.3%B.
Embodiment 6
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid is：Nickel sulfate 280g/L, nickel chloride 45g/L, cobaltous sulfate 45g/L, sodium borohydride 3.5g/L, ethylenediamine
55g/L, buffer 48g/L.
The pH value of the electroplate liquid is 13, and temperature is 65 DEG C；
The copper plate base body is negative electrode, and nickel bead is anode, and the make-to-break ratio of pulse plating is 1：6, average current density 3.5A/
dm2。
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：65.6%Ni, 31.2%Co and 3.2%B.
Embodiment 7
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 1：
The composition of electroplate liquid, in terms of mass concentration, it is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, hydroboration
Sodium 2.5g/L, ethylenediamine 40g/L, buffer 40g/L, wetting agent MT-80 0.04g/L.
The buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
Embodiment 8
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 2：
The composition of electroplate liquid, in terms of mass concentration, it is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, hydroboration
Sodium 2.5g/L, ethylenediamine 40g/L, buffer 40g/L, wetting agent MT-80 0.01g/L.
The buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
Embodiment 9
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, as different from Example 3：
The composition of electroplate liquid, in terms of mass concentration, it is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, hydroboration
Sodium 2.5g/L, ethylenediamine 40g/L, buffer 40g/L, MT-80 0.1g/L.
The buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
Embodiment 10
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, wherein, electroplate liquid composition and electricity
Plating condition with embodiment 1, except that：
Copper plate of crystallizer after plating is placed in vacuum drying oven, vacuum is 5.0 × 10-3Pa, 3h is heat-treated at 350 DEG C.
Comparative example 1
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 255g/L, cobaltous sulfate 30g/L, sodium borohydride 2.5g/L, ethylenediamine 40g/L, buffer
40 g/L。
The comparative example omits nickel chloride, and nickel salt total amount is identical with the embodiment of the present invention 1.
Comparative example 2
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 220g/L, nickel sulfamic acid 35g/L, sulfamic acid cobalt 30g/L, sodium borohydride 2.5g/
L, ethylenediamine 40g/L, the g/L of buffer 40.
The comparative example have adjusted the species of nickel salt, cobalt salt.
Comparative example 3
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, dimethyamine borane 2.5g/L, second
Diamines 40g/L, buffer 40g/L.
The comparative example substitutes sodium borohydride with dimethyamine borane.
Comparative example 4
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, sodium borohydride 2.5g/L, ethylenediamine
40g/L, buffer 40g/L, sodium 2-ethylhexyl sulfate 0.04g/L.
The comparative example substitutes wetting agent MT-80 with dodecyl sodium sulfate.
Comparative example 5
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, sodium borohydride 2.5g/L, ethylenediamine
40g/L。
The comparative example omits buffer.
Comparative example 6
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 220g/L, nickel chloride 35g/L, cobaltous sulfate 30g/L, sodium borohydride 2.5g/L, diethylamine
40g/L, the g/L of boric acid 40.
The comparative example buffer uses boric acid.
Comparative example 7
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 120g/L, nickel chloride 10g/L, cobaltous sulfate 60g/L, sodium borohydride 5g/L, ethylenediamine
40g/L, buffer 40g/L.
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：40.2%Ni, 53.1%Co and 6.7%B.
Comparative example 8
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The composition of electroplate liquid is：Nickel sulfate 350g/L, nickel chloride 60g/L, cobaltous sulfate 3g/L, sodium borohydride 0.5g/L, ethylenediamine
40g/L, buffer 40g/L.
The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：73.6%Ni, 25.6%Co and 0.8%B.
Comparative example 9
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The make-to-break ratio of pulse plating is 1：8, average current density 5A/dm2。
Comparative example 10
The electro-plating method of the present embodiment continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, specific steps and phase of the present invention
Together, except that：
The pH value of electroplate liquid is 7.5.
To embodiment 1 ~ 3,7 ~ 10 and the hardness of the gained copper plate of crystallizer of comparative example 1 ~ 10, porosity, decay resistance, resistance to
Mill performance, bond strength are measured, and count a steel transportation amount of copper plate of crystallizer, as a result as shown in Table 1 and Table 2.
Assay method：
Hardness test：Using microhardness testers, the hardness of coating is tested under 100g on-load pressure, often built-in testing 5 times, removes
Maxima and minima, then to 3 results averageds, table look-up and try to achieve coating Vickers hardness number HV；
Corrosion resistance is tested：Sample is cut into about 10mm × 10mm square, by matrix and side epoxy encapsulation, immersion
In 20ml1：In 1 hydrochloric acid, sealing determines the content of Ni, Co, B in corrosive liquid after 15 days, represented with total stripping quantity mg；
Wearability test：The abrasion test of coating is carried out on ring block type abrasion tester, standard friction inner loop sample wheel material
For 45# steel, quenched processing, friction environment temperature is room temperature, and loading 20N, friction inner loop rotating speed is 105 ~ 120r/min, friction
Shi Changwei 8 hours, represented with wear weight loss speed mg/h；
Bond strength is tested：Refering to the method announced in document（Zhang Hongjie, Wen Maoyuan, Hou Zhen, it is inner to reach crystallizer copper plate coatings
Measure [J] sufacings of interface bond strength, 06 month the 3rd phase of volume 43 in 2014）, represented with MPa.
The measurement result of the embodiment 1 ~ 3,7 ~ 10 of table 1
| Embodiment/project | 1 | 2 | 3 | 7 | 8 | 9 | 10 |
| Hardness/HV | 1024 | 925 | 906 | 1050 | 955 | 932 | 1895 |
| Corrosion resistance/mg | 0.15 | 0.20 | 0.21 | 0.13 | 0.19 | 0.20 | 0.13 |
| Wearability/mgh-1 | 1.2 | 1.5 | 1.6 | 1.0 | 1.3 | 1.4 | 0.8 |
| Bond strength/MPa | 571 | 552 | 557 | 578 | 561 | 563 | 602 |
| Steel transportation amount/ten thousand ton | 18 | 17 | 16 | 18 | 17 | 17 | 20 |
The result of table 1 is shown：The stripping quantity of Ni-Co-B alloy layers of the present invention is less than 0.25mg, excellent corrosion-proof performance；The present invention
The wear weight loss speed of Ni-Co-B alloy layers is less than 2.0mg/h, and abrasion resistance properties are good；Hardness is up to more than 1000HV, warp
After vacuum heat, hardness can reach more than 1800HV；Bond strength is more than 550MPa, good with copper plate of crystallizer binding ability
Good, a steel transportation amount is more than 150,000 tons.
The measurement result of the comparative example 1 ~ 10 of table 2
| Comparative example/project | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Hardness/HV | 772 | 790 | 813 | 801 | 762 | 801 | 530 | 645 | 785 | 690 |
| Corrosion resistance/mg | 0.23 | 0.24 | 0.35 | 0.30 | 0.25 | 0.23 | 0.43 | 0.54 | 0.35 | 0.65 |
| Wearability/mgh-1 | 2.7 | 2.2 | 3.4 | 1.9 | 2.5 | 2.1 | 5.1 | 6.0 | 2.0 | 5.3 |
| Bond strength/MPa | 502 | 521 | 470 | 485 | 452 | 473 | 430 | 402 | 460 | 320 |
| Steel transportation amount/ten thousand ton | 14 | 15 | 12 | 13 | 10 | 12 | 7 | 9 | 11 | 10 |
The result of table 2 is shown：The electroplate liquid composition or plating conditions for changing the present invention close to copper plate of crystallizer electroplated Ni-Co-B
The performance of gold plate has different degrees of influence.
Comparative example 1：Compared with Example 1, eliminate the use of nickel chloride, nickel salt only with nickel sulfate, measurement result with
Embodiment 1 compares：Hardness declines about 25%, and stripping quantity increase 0.08mg, wear weight loss speed is added more than 1 times, bond strength
Reduce by 69 MPa, a steel transportation amount reduces 40,000 tons, and every Testing index has decline, shows the selection of nickel salt species to Ni-
The material impact of Co-B alloy layer performances.
Comparative example 2：Compared with Example 1, nickel chloride is substituted with nickel sulfamic acid, cobaltous sulfate is substituted with sulfamic acid cobalt,
Compared with Example 1, the hardness of Ni-Co-B alloy layers reduces 234HV to measurement result, and stripping quantity increases by 0.09 mg, and abrasion is lost
Weight speed increases by 0.7 mg/h, and bond strength reduces by 50 MPa, poor compared with embodiment 1, shows the selection of nickel salt, cobalt salt species
With the material impact arranged in pairs or groups to Ni-Co-B alloy layer performances.
Comparative example 3：Compared with Example 1, sodium borohydride is only substituted with dimethyamine borane, measurement result is shown, wear-resisting
Property, bond strength decline and protrude, wear weight loss speed increases by 2.2 mg/h, and bond strength is down to 470 MPa by 571 MPa, one
Secondary steel transportation amount reduces 60,000 tons, shows that present invention selection sodium borohydride is matched somebody with somebody as boron element source and electroplate liquid composition and condition
Close the raising for being advantageous to Ni-Co-B alloy layer performances.
Comparative example 4：Compared with Example 1, wetting agent MT-80, Ni-Co-B Alloy Plating is only substituted with dodecyl sodium sulfate
Hardness, corrosion resistance, wearability, the bond strength of layer have declined, and the deterioration of corrosion resistance and bond strength is particularly evident,
Show that wetting agent MT-80 serves reduction surface tension really, improve surface quality, the effect such as internal stress is reduced, to enhancing
The corrosion resistance and bond strength of Ni-Co-B alloy layers of the present invention have the function that important.
Comparative example 5：The use of buffer is omitted, buffer can improve coating surface quality, improve coating properties,
After omission, as a result show, the hardness of Ni-Co-B alloy layers, corrosion resistance, wearability and bond strength are had a significant impact.
Comparative example 6：Compared with embodiment 1 using boric acid as buffer, known boric acid has the function that to buffer and is complexed, and as a result shows
Show, compared with the comparative example 5 for not using buffer, although the performance of Ni-Co-B alloy layers increases, effect increase is simultaneously
Not significantly, and compared with Example 1 compared with the properties significant difference of Ni-Co-B alloy layers.
Comparative example 7 and comparative example 8：It has adjusted the content of nickel sulfate, nickel chloride, cobaltous sulfate and sodium borohydride simultaneously respectively,
The composition of gained Ni-Co-B alloy layers forms：40.2%Ni, 46.9%Co, 6.7%B and 73.6%Ni, 25.6%Co and
0.8%B, formed with the claimed Ni-Co-B alloy layers of the present invention（50% ~ 70%Ni, 30% ~ 45%Co and 1% ~ 5%B）Difference,
Measurement result is shown：Hardness, corrosion resistance, wearability and the bond strength of Ni-Co-B alloy layers, which exist, to be remarkably decreased, once
Steel transportation amount absolutely proves property of the Ni-Co-B alloy layers composition composition of the present invention to Ni-Co-B alloy layers less than 100,000 tons
There can be material impact, only can just play good synergistic effect when each composition assembles proper.
Comparative example 9：Changing plating conditions is：The make-to-break ratio of pulse plating is 1：8, average current density 5A/dm2, survey
Determine result to show：Compared with embodiment 1, the hardness of Ni-Co-B alloy layers reduces 239 HV, corrosion resistance：Stripping quantity increases 0.20mg,
Wearability：Wear weight loss speed increases by 0.8 mg/h, and bond strength reduces by 111 MPa, illustrates that suitable plating conditions are more favourable
In the high performance Ni-Co-B alloy layers of acquisition.
Comparative example 10：Changing plating conditions is：The pH value of electroplate liquid is 7.5, and measurement result is shown：It is every compared with embodiment 1
Hydraulic performance decline is notable, illustrates that the suitable pH value of electroplate liquid has material impact to obtaining high performance Ni-Co-B alloy layers.On
The result for stating each comparative example is shown, the single a certain or some condition for conventionally changing the present invention, can not be obtained pre-
The Ni-Co-B alloy layers of phase performance, show that electroplate liquid of the present invention assembles rationally, plating conditions are suitable, coordinated, finally obtain
Obtained high performance Ni-Co-B alloy layers.
Although the foregoing describing the embodiment of the present invention, those familiar with the art should manage
Solution, the specific embodiment described by us are merely exemplary, rather than for the restriction to the scope of the present invention, are familiar with this
The equivalent modification and change that the technical staff in field is made in the spirit according to the present invention, should all cover the present invention's
In scope of the claimed protection.
Claims (10)
- A kind of 1. electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers, it is characterised in that：With mass concentration Meter, composition include：170 ~ 350g/L of nickel salt, 5 ~ 50g/L of cobalt salt, 0.5 ~ 4g/L of sodium borohydride, 20 ~ 60g/L of ethylenediamine, buffer 30~50g/L。
- 2. the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 1, its feature exist In：The nickel salt is the composition of nickel sulfate and nickel chloride, wherein：150 ~ 300g/L of nickel sulfate, 20 ~ 50g/L of nickel chloride.
- 3. the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 1, its feature exist In：The cobalt salt is cobaltous sulfate.
- 4. the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 1, its feature exist In：The buffer is sodium potassium tartrate tetrahydrate and ammonium citrate in mass ratio 1：The mixture of 1 composition.
- 5. the electroplate liquid of the continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as described in any one of claim 1 ~ 4, its It is characterised by：The electroplate liquid composition also includes：0.01 ~ 0.1g/L of surfactant.
- 6. the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 5, its feature exist In：The pH value of the electroplate liquid is 9 ~ 14.
- 7. the plating side of the electroplate liquid using the continuous casting crystallizer copper plate deposit N i-Co-B alloy layers described in claim 6 Method, it is characterised in that：It is that the copper plate base body by pretreatment is placed in the electroplate liquid, using pulse plating, with the copper Plate matrix, using nickel bead as anode, carries out negative electrode plating as negative electrode.
- 8. the electro-plating method of the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 7, It is characterized in that：The make-to-break ratio of the pulse plating is 1：6, average current density is 1 ~ 4 A/dm2。
- 9. the electro-plating method of the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 8, It is characterized in that：The temperature of the pulse plating is 55 ~ 70 DEG C.
- 10. the plating side of the electroplate liquid of continuous casting crystallizer copper plate deposit N i-Co-B alloy layers as claimed in claim 9 Method, it is characterised in that：The composition of the Ni-Co-B alloy layers, is calculated in mass percent, is：50% ~ 69%Ni, 30% ~ 45%Co And 1% ~ 5%B.
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