CN104985147A - High-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board and preparation technology thereof - Google Patents
High-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board and preparation technology thereof Download PDFInfo
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Abstract
The invention relates to the field of electroplate technology used for surface treatment. A high-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board comprises a crystallizer copper board substrate, the surface of the copper board substrate is plated with a Ni-Co-Fe alloy clad layer, and the Ni-Co-Fe alloy clad layer comprises 65 to 78 wt% Ni, 20 to 30 wt% Co and 2 to 5 wt% Fe. The high-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board is particularly apply to a continuous caster whose casting speed is 1.5 to 2.0 m/min, in particular, the Ni-Co-Fe alloy clad layer is good in self-lubricity, high corrosion resistance and abrasion resistance at high temperature, the service life of the continuous casted crystallizer copper board is raised by 2.6 times compared with a common Ni-Co alloy clad layer, the cost for maintaining the crystallizer copper board can be reduced by 20 to 30 %, and the continuous casting work rate is raised by approximately 1.2 times.
Description
Technical field
The present invention relates to plating surface treatment technical field, be specifically related to a kind of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate and preparation technology thereof.
Background technology
The core apparatus that crystallizer is produced as whole steel-making direct casting; the quality of crystallizer quality directly has influence on the operating rate of slab quality and conticaster; the molten steel of boiling and the covering slag liquid of melting directly contact copper plate of crystallizer surface cool and become strand; and along with the sliding friction between inwall and strand; there is better thermal conductivity on severe operating environment requirements copper plate of crystallizer surface; higher mechanical strength, the wearability that will have well and corrosion resisting property.
In recent years, along with the development of the technology such as the maximization of continuous casting installation for casting, high pulling rate and on-line width adjustment, the significantly raising of continuous casting work rate, in the past single pure Ni coating, Ni-Co coating, hardness is low, not wear-resistant, one time steel transportation amount is undesirable, Ni-Fe coating poor chemical stability, and fragility is high and toughness is low, easily fire check is produced under high temperature, be only applicable to lower pulling rate (pulling rate is no more than 0.8m/min) conticaster, although some new and high technologies are arisen at the historic moment on copper plate of crystallizer, investment is large, cost is high, still fails to meet the needs of enterprise's production development.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, one is provided to overcome continuous casting crystallizer copper plate steel transportation amount under high pulling rate 1.5 ~ 2.0m/min low, the wearing and tearing of copper coin bottom are large, repair deficiency often, a kind of Ni-Co-Fe alloy layer continuous casting crystallizer copper plate and preparation technology thereof are provided, good to obtain with copper plate base body adhesion, hardness is high, the Ni-Co-Fe alloy layer that oxidation resistance is strong, this alloy microstructure is tight, anti-wear performance is superior, particularly self lubricity at high temperature, high corrosion-resistant and mar proof good, significantly improve the service life of continuous casting crystallizer copper plate.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, comprise crystallizer copper board substrate, the surface of described copper plate base body is coated with Ni-Co-Fe alloy layer, and described Ni-Co-Fe alloy layer contains 65 ~ 78wt%Ni, 20 ~ 30wt%Co and 2 ~ 5wt%Fe.
Further, described Ni-Co-Fe alloy layer contains 70wt%Ni, 25wt%Co and 5wt%Fe.
Further, the thickness of described Ni-Co-Fe alloy layer is 0.2 ~ 4.0mm.
Present invention also offers a kind of preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, comprise the following steps:
A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating.
Further, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：750~900g/L；
NiCl
2·6H
2O：10~35g/L；
Fe（NH
2SO
3）
2·4H
2O：3~12g/L；
Co（NH
2SO
3）
2·4H
2O：18~60g/L；
H
3BO
3：22~35g/L；
Low foam wetting agent: 15 ~ 30g/L;
Additive: 60-150mL/L.
Further, described electroplating technique condition is:
PH value: 3.8 ~ 5.0;
Temperature of electroplating solution: 55 ~ 65 DEG C;
Current density: 1 ~ 13A/dm
2;
Agitating mode is: compressed air stirs and auxiliary stirring.
Wherein, described auxiliary stirring can adopt large discharge filter to carry out auxiliary stirring; Described stirring is advisable for more than 7 times to make electroplate liquid circulation per hour, and preferred cycle number of times is 7 times.
Preferably, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：800g/L；
NiCl
2·6H
2O：25g/L；
Fe（NH
2SO
3）
2·4H
2O：7g/L；
Co（NH
2SO
3）
2·4H
2O：40g/L；
H
3BO
3：28g/L；
Low foam wetting agent: 20g/L;
Additive: 100mL/L.
Further, the preferred ethylhexyl sulfate of described low foam wetting agent.
Further, one or both in the preferred asccharin of described additive, pyridinium propane sulfonic acid inner salt.
The present invention is at the electroplating surface Ni-Co-Fe alloy layer of copper plate of crystallizer, coating surface is non-microcracked, there is good corrosion resistance and wearability, basal body binding force is good, and internal performance is superior, and energy consumption is low, simple to operate, solve in the past that continuous casting crystallizer copper plate steel transportation amount under pulling rate 1.5 ~ 2.0m/min is low well, the wearing and tearing of copper coin bottom are large, repair defect often.
The continuous casting crystallizer copper plate of Ni-Co-Fe alloy layer of the present invention is specially adapted to conticaster that pulling rate is 1.5 ~ 2.0m/min uses, and known, pulling rate determines the production efficiency of conticaster.But high pulling rate and strand high-quality conflicting often.The present inventor is by exploring for many years and summing up, system research and control is carried out from aspects such as electroplate liquid composition, electroplating technology, practice effects, obtain the copper plate of crystallizer of the equal comparative superiorities of various aspects of performance such as hardness, bond strength, wear-resisting, decay resistance, in long-term practice, also achieve satisfied effect, thus effectively guarantee the quality problems of strand under high pulling rate.
Known, the coating of good combination property be expected, must control current density, pH value and electroplating temperature etc. well.In any electroplating technology, if the too small meeting of current density causes liberation of hydrogen serious, current density is crossed conference and is caused that coating is discontinuous, jaundice.PH value also will control in suitable scope, and the pH value of plating solution directly affects cathodic polarization curve, and pH value is larger, cathodic polarization rate is higher, and the tendency of electrode polarization is also larger, and pH value affects the liberation of hydrogen degree of negative electrode simultaneously, pH value is lower, and on negative electrode, liberation of hydrogen becomes easier.Temperature is especially great on electroplating quality impact, because Ni-Co-Fe alloy electroplating bath poor stability, temperature influence is comparatively large, and the performance (brightness and corrosion resistance) of bath temperature to electrodeposition process and coating has material impact.Raise bath temperature, can make on negative electrode be deposited on lower overpotential under carry out; The corrosion resistance of coating that bath temperature obtains 50 ~ 65 DEG C time and hardness best, and close with chrome plating.
And the preparation technology of the electroplating surface Ni-Co-Fe alloy layer of copper plate of crystallizer of the present invention belongs to the process for cleanly preparing of low energy consumption and low material consumption, and the feature of environmental protection is good, without sewage discharge.The defects such as test shows, adopts present invention process condition, and the Ni-Co-Fe alloy layer on copper plate of crystallizer surface free of pinholes, needle-like in electroplating process is loose, technical process is easy to control, good operation stability, the associativity of coating and copper plate base body is good, and thickness of coating can reach 4.0mm.The copper plate of crystallizer of Ni-Co-Fe alloy layer of the present invention is specially adapted to 1.5 ~ 2.0m/min casting speed continuous casting machine uses, especially, Ni-Co-Fe alloy layer self lubricity at high temperature, high corrosion-resistant and excellent abrasion resistance, raising about 2.6 times compared with conventional nickel cobalt in service life of continuous casting crystallizer copper plate, decrease the maintenance cost about 20 ~ 30% of copper plate of crystallizer, improve continuous casting work rate about 1.2 times.
Detailed description of the invention
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, comprise crystallizer copper board substrate, the surface of described copper plate base body is coated with Ni-Co-Fe alloy layer;
In the present invention, described Ni-Co-Fe alloy layer contains 65 ~ 78wt%Ni, 20 ~ 30wt%Co and 2 ~ 5wt%Fe; By controlling the ratio of Ni, Co, Fe in plating solution, and under the synergy of other solution composition, the part by weight of Ni, Co, Fe in coating can be controlled, preparing the coating of excellent performance of the present invention.
In the present invention, described Ni-Co-Fe alloy layer is preferred. containing 70wt%Ni, 25wt%Co and 5wt%Fe.
In the present invention, the thickness of described Ni-Co-Fe alloy layer is 0.2 ~ 4.0mm, and preferably 3.0 ~ 4.0 ㎜, both can increase the anti-wear performance of coating, also have excellent heat conductivility simultaneously.
Present invention also offers a kind of preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, carry out according to the following steps:
A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of: Ni(NH
2sO
3)
24H
2o:750 ~ 900g/L, NiCl
26H
2o:10 ~ 35g/L, Fe(NH
2sO
3)
24H
2o:3 ~ 12g/L, Co(NH
2sO
3)
24H
2o:18 ~ 60g/L, H
3bO
3: 22 ~ 35g/L, low foam wetting agent: 15 ~ 30g/L, additive: 60-150mL/L;
Wherein, the preferred ethylhexyl sulfate of described low foam wetting agent.
One or both in the preferred asccharin of described additive, pyridinium propane sulfonic acid inner salt.
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area; In this step, grease cleaning, the activation of mechanical sandblasting plucking, electrolytic degreasing, Ultrasonic Cleaning and acid solution spray are routine techniques, and concrete technological parameter and implementation method are prior art;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating;
Wherein, described electroplating technology is: the pH value of electroplate liquid controls 3.8 ~ 5.0; The temperature of electroplate liquid maintains 55 ~ 65 DEG C; Current density in electroplating process is 1 ~ 13A/dm
2; Electroplate liquid agitating mode is that compressed air stirs and auxiliary stirring.
Preferably, electroplate liquid of the present invention consists of: Ni(NH
2sO
3)
24H
2o:800g/L, NiCl
26H
2o:25g/L, Fe(NH
2sO
3)
24H
2o:7g/L, Co(NH
2sO
3)
24H
2o:40g/L, H
3bO
3: 28g/L, low foam wetting agent: 20g/L, additive: 100mL/L;
Wherein, the preferred ethylhexyl sulfate of low foam wetting agent; Additive is asccharin and pyridinium propane sulfonic acid inner salt.
Ni(NH in the present invention
2sO
3)
24H
2o, NiCl
26H
2o, Fe(NH
2sO
3)
24H
2o, Co(NH
2sO
3)
24H
2o, H
3bO
3, low foam wetting agent, additive all can commercially availablely obtain.
In order to further illustrate the present invention, below in conjunction with embodiment, high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate provided by the invention and preparation technology thereof are described in detail.
Embodiment 1
High pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention, realized by following preparation technology, concrete steps are: A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：800g/L；
NiCl
2·6H
2O：25g/L；
Fe（NH
2SO
3）
2·4H
2O：7g/L；
Co（NH
2SO
3）
2·4H
2O：40g/L；
H
3BO
3：28g/L；
Ethylhexyl sulfate: 20g/L;
Asccharin and pyridinium propane sulfonic acid inner salt: 100mL/L; The preferred 1:1.5 of volume ratio of described asccharin and pyridinium propane sulfonic acid inner salt.
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating; Described electroplating technology is:
PH value: 4.0;
Temperature of electroplating solution: 55 DEG C;
Current density: 5A/dm
2;
Agitating mode is: compressed air stirs and large discharge filter is auxiliary stirs; Electroplate liquid cycle-index hourly is 7 times.
By above-mentioned technique, establish Ni-Co-Fe alloy layer at the plated surface of crystallizer copper board substrate, wherein Ni-Co-Fe alloy layer contains 70wt%Ni, 25wt%Co and 5wt%Fe.
In the present embodiment, the thickness of described Ni-Co-Fe alloy layer is 4.0mm.
Embodiment 2
High pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention, realized by following preparation technology, concrete steps are: A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：750g/L；
NiCl
2·6H
2O：10g/L；
Fe（NH
2SO
3）
2·4H
2O：3g/L；
Co（NH
2SO
3）
2·4H
2O：18g/L；
H
3BO
3：22g/L；
Ethylhexyl sulfate: 15g/L;
Asccharin: 60mL/L;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating; Described electroplating technology is:
PH value: 3.8;
Temperature of electroplating solution: 60 DEG C;
Current density: 1A/dm
2;
Agitating mode is: compressed air stirs and large discharge filter is auxiliary stirs, and electroplate liquid cycle-index hourly is 8 times.
By above-mentioned technique, establish Ni-Co-Fe alloy layer at the plated surface of crystallizer copper board substrate, wherein Ni-Co-Fe alloy layer contains 65wt%Ni, 30wt%Co and 5wt%Fe.
In the present embodiment, the thickness of described Ni-Co-Fe alloy layer is 0.2mm.
Embodiment 3
High pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention, realized by following preparation technology, concrete steps are: A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：900g/L；
NiCl
2·6H
2O：35g/L；
Fe（NH
2SO
3）
2·4H
2O：12g/L；
Co（NH
2SO
3）
2·4H
2O：60g/L；
H
3BO
3：35g/L；
Ethylhexyl sulfate: 30g/L;
Pyridinium propane sulfonic acid inner salt: 150mL/L;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating; Described electroplating technology is:
PH value: 5.0;
Temperature of electroplating solution: 65 DEG C;
Current density: 10A/dm
2;
Agitating mode is: compressed air stirs and large discharge filter is auxiliary stirs, and electroplate liquid cycle-index hourly is 8 times.
By above-mentioned technique, establish Ni-Co-Fe alloy layer at the plated surface of crystallizer copper board substrate, wherein Ni-Co-Fe alloy layer contains 78wt%Ni, 20wt%Co and 2wt%Fe.
In the present embodiment, the thickness of described Ni-Co-Fe alloy layer is 3.5mm.
Embodiment 4
High pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention, realized by following preparation technology, concrete steps are: A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：850g/L；
NiCl
2·6H
2O：30g/L；
Fe（NH
2SO
3）
2·4H
2O：10g/L；
Co（NH
2SO
3）
2·4H
2O：50g/L；
H
3BO
3：32g/L；
Ethylhexyl sulfate: 25g/L;
Asccharin and pyridinium propane sulfonic acid inner salt: 120mL/L, the volume ratio of asccharin and pyridinium propane sulfonic acid inner salt is 1:1.2;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating; Described electroplating technology is:
PH value: 4.5;
Temperature of electroplating solution: 58 DEG C;
Current density: 8A/dm
2;
Agitating mode is: compressed air stirs and large discharge filter is auxiliary stirs, and electroplate liquid cycle-index hourly is 7 times.
By above-mentioned technique, establish Ni-Co-Fe alloy layer at the plated surface of crystallizer copper board substrate, wherein Ni-Co-Fe alloy layer contains 72wt%Ni, 25wt%Co and 3wt%Fe.
In the present embodiment, the thickness of described Ni-Co-Fe alloy layer is 3.0mm.
Embodiment 5
High pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention, realized by following preparation technology, concrete steps are: A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid, described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：780g/L；
NiCl
2·6H
2O：18g/L；
Fe（NH
2SO
3）
2·4H
2O：5g/L；
Co（NH
2SO
3）
2·4H
2O：30g/L；
H
3BO
3：25g/L；
Ethylhexyl sulfate: 18g/L;
Asccharin and pyridinium propane sulfonic acid inner salt: 80mL/L; The volume ratio of asccharin and pyridinium propane sulfonic acid inner salt is 1:1;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating; Described electroplating technology is:
PH value: 4.2;
Temperature of electroplating solution: 62 DEG C;
Current density: 13A/dm
2;
Agitating mode is: compressed air stirs and large discharge filter is auxiliary stirs, and electroplate liquid cycle-index hourly is 9 times.
By above-mentioned technique, establish Ni-Co-Fe alloy layer at the plated surface of crystallizer copper board substrate, wherein Ni-Co-Fe alloy layer contains 68wt%Ni, 28wt%Co and 4wt%Fe.
In the present embodiment, the thickness of described Ni-Co-Fe alloy layer is 1.5mm.
Comparative example 1
Patent CN 1031894 provides the method for ferro-nickel alloy electroplating on a kind of crystallizer copper plate of plate blank continuous casting machine, and this comparative example uses the embodiment 1 in this patent text, and concrete electroplate liquid consists of:
Nickelous sulfate (NiSO
47H
2o): 180g/L;
Nickel chloride (NiCl
26H
2o): 14g/L;
Boric acid (H
3bO
3): 35g/L;
Ferrous sulfate (FeSO
47H
2o): 2.5g/L;
Lauryl sodium sulfate: 0.08g/L;
Additive T1:6mL/L;
Additive T2:8mL/L;
Concrete electroplating technology is: electrolysis temperature: 56 DEG C; PH value: 2.8; Current density: 2.5A/dm
2; Agitating mode is: reciprocation type movable cathode, and speed is 1m/min.
Comparative example 2
At the electroplating surface nickel coating of copper plate of crystallizer, the composition of this electroplate liquid and electroplating technology are all with reference to prior art.
The hardness of embodiment 1 ~ 5 gained copper plate of crystallizer and comparative example 1,2 gained copper plate of crystallizer, porosity, decay resistance and bond strength etc. are measured or evaluated, as shown in table 1.
Table 1 experimental result
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Hardness HV | 574 | 465 | 548 | 559 | 521 | 326 | 188 |
| Porosity, % | 0.01 | 0.03 | 0.02 | 0.015 | 0.02 | 0.10 | 0.08 |
| Rate of corrosion in 10%HCl, mg/m 2·h | 2.65 | 2.92 | 2.91 | 2.78 | 2.89 | 4.78 | 6.84 |
| 10%H 2SO 4Middle rate of corrosion mg/m 2·h | 2.59 | 2.81 | 2.80 | 2.70 | 2.78 | 4.35 | 6.47 |
| Bond strength, N/mm 2 | 473 | 445 | 451 | 458 | 448 | 310 | 261 |
| Steel-passing amount (low middle pulling rate), ten thousand tons | 18 | 11 | 12 | 16 | 15 | 8 | 4 |
As can be seen from Table 1, the hardness of Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention is more than 1.4 times of comparative example 1, is more than 2.5 times of comparative example 2, illustrates that the hardness of Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention increases significantly; Porosity of the present invention is significantly less than comparative example 1 and comparative example 2; Under equal conditions, in the 10%HCl of copper plate of crystallizer of the present invention, rate of corrosion is minimum is only 55.4% of comparative example 1, and be 38.7% of comparative example 2, tool has clear improvement, the 10%H of copper plate of crystallizer of the present invention
2sO
4middle rate of corrosion also tool is significantly improved; The bond strength of Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention is 1.4 ~ 1.5 times of comparative example 1, and be 1.6 ~ 1.7 times of comparative example 2, bond strength has remarkable lifting; For the slab caster of pulling rate 1.5 ~ 2.0m/min, the average steel-passing amount of crystallizer of Ni-Co-Fe alloy layer continuous casting crystallizer copper plate of the present invention is used to have obvious rising.
Claims (8)
1. one kind high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, comprise crystallizer copper board substrate, it is characterized in that: the surface of described copper plate base body is coated with Ni-Co-Fe alloy layer, described Ni-Co-Fe alloy layer contains 65 ~ 78wt%Ni, 20 ~ 30wt%Co and 2 ~ 5wt%Fe.
2. high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as claimed in claim 1, is characterized in that: the thickness of described Ni-Co-Fe alloy layer is 0.2 ~ 4.0mm.
3. a preparation technology for high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate, is characterized in that: it comprises the following steps:
A, preparation electroplate liquid: in electrolytic cell, prepare electroplate liquid;
B, treatment before plating: after described copper plate base body is carried out fine finishining, carry out grease cleaning, mechanical sandblasting plucking, electrolytic degreasing and Ultrasonic Cleaning successively, insulation electroless coating region, installs plating PVC board cathodic protection frock, acid solution spray activation copper coin plating area;
C, electroplated Ni-Co-Fe alloy layer: electroplate in the electroplate liquid prepared in described step A by the copper plate of crystallizer after described step B process, after Ni-Co-Fe alloy layer electroplating time reaches technological requirement electroplating time, stop plating.
4. the preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as claimed in claim 3, is characterized in that: described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：750~900g/L；
NiCl
2·6H
2O：10~35g/L；
Fe（NH
2SO
3）
2·4H
2O：3~12g/L；
Co（NH
2SO
3）
2·4H
2O：18~60g/L；
H
3BO
3：22~35g/L；
Low foam wetting agent: 15 ~ 30g/L;
Additive: 60-150mL/L.
5. the preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as claimed in claim 4, is characterized in that: described low foam wetting agent is ethylhexyl sulfate.
6. the preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as claimed in claim 4, is characterized in that: described additive is one or both in asccharin, pyridinium propane sulfonic acid inner salt.
7. the preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as described in claim 4 or 5 or 6, is characterized in that: described electroplate liquid consists of:
Ni（NH
2SO
3）
2·4H
2O：800g/L；
NiCl
2·6H
2O：25g/L；
Fe（NH
2SO
3）
2·4H
2O：7g/L；
Co（NH
2SO
3）
2·4H
2O：40g/L；
H
3BO
3：28g/L；
Ethylhexyl sulfate: 20g/L;
Asccharin and pyridinium propane sulfonic acid inner salt: 100mL/L, the volume ratio of described asccharin and pyridinium propane sulfonic acid inner salt is 1:1.5.
8. the preparation technology of high pulling rate Ni-Co-Fe alloy layer continuous casting crystallizer copper plate as claimed in claim 3, is characterized in that: described electroplating technique condition is:
PH value: 3.8 ~ 5.0;
Temperature of electroplating solution: 55 ~ 65 DEG C;
Current density: 1 ~ 13A/dm
2;
Agitating mode is: compressed air stirs and auxiliary stirring.
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