WO2020233026A1 - 结晶器铜板及其分层电镀工艺 - Google Patents

结晶器铜板及其分层电镀工艺 Download PDF

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WO2020233026A1
WO2020233026A1 PCT/CN2019/119573 CN2019119573W WO2020233026A1 WO 2020233026 A1 WO2020233026 A1 WO 2020233026A1 CN 2019119573 W CN2019119573 W CN 2019119573W WO 2020233026 A1 WO2020233026 A1 WO 2020233026A1
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copper plate
plane
nickel
layer
plating layer
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PCT/CN2019/119573
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English (en)
French (fr)
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王硕煜
丁贵军
朱广宏
丁毅
张龙
杭志明
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安徽马钢表面技术股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/057—Manufacturing or calibrating the moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • 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

Definitions

  • the invention relates to the field of electroplating technology, in particular to the electroplating technology of crystallizer copper plates.
  • Mold copper plates are used in continuous casting machines in iron and steel metallurgy and are the core components of continuous casting. Mold copper plates are an important heat-conducting component for continuous casting from liquid steel to solidification into a solid slab. Its quality directly affects the quality of the cast slab. Surface quality, continuous casting machine drawing speed and other indicators. The molten steel flows through the copper plate of the mold, crystallizes into a billet under the action of external cooling water, and is pulled out of the mold by the ingot bar.
  • the molten steel is liquid at the upper mouth of the copper plate of the mold, and a layer of blank shell is formed on the back surface of the lower mouth.
  • the upper mouth of the mold copper plate bears the high temperature of the molten steel and the lower mouth bears Wear of the billet.
  • the continuous casting machine requires high single pass steel throughput and fast drawing speed during work, so the surface quality of the mold copper plate is very high.
  • the upper and lower plating layer of the mold copper plate is required to have stable thermal deformation resistance under high temperature conditions, and the lower mouth plating layer of the mold copper plate is required to have good wear resistance under the wear of the steel billet. Therefore, the copper plate coating of the general mold requires a low upper mouth hardness for thermal resistance, and a high lower mouth hardness for wear resistance.
  • the surface of common mold copper plate adopts a single plating layer, and the copper plate surface is electroplated with a layer of nickel, nickel-iron, nickel-cobalt, cobalt-nickel and other plating layers.
  • a plating layer cannot take into account the low hardness of the upper mouth and the high hardness requirements of the lower mouth. After reaching the ideal number of through-steel furnaces, there will be a large amount of wear on the lower mouth or hot cracks on the upper mouth or even the coating peeling off.
  • the patent application No. 201210269246.X discloses a high-speed continuous casting machine mold copper plate electroplating process.
  • the upper and lower mouths are different.
  • the surface properties of, in which the upper surface is high temperature resistant coating, and the lower surface is wear resistant coating.
  • the starting point of the solution is to adjust the electroplating solution, and obtain different surfaces by electroplating at the two ends, thereby solving the above-mentioned problems.
  • the above solution will result in two structures on the bonding surface of the plating layer, and it is easy to form a hard injury area at the junction of the two structures, cracking and peeling.
  • the patent application No. 201210269259.7 discloses an electrolytic cell formed by electroplating the upper and lower layers of the crystallizer copper plate at one time, hoping to solve the problem of two electroplating mentioned in the previous patent method at one time through the structure of the electrolytic cell.
  • the upper and lower opening directions of the mold copper plate in this patent are inconsistent during electroplating and actual use, resulting in the electroplated surface that does not meet the actual use requirements; and the film used in the electrolytic cell will make the surface of the mold copper plate corresponding The location cannot be electroplated, so there is a gap, which affects the surface quality of the mold copper plate.
  • the purpose of the present invention is to provide a mold copper plate, which adopts a new electroplating process, which solves the problem that the traditional consistent mold copper plate surface upper and lower mouth performance cannot meet different requirements, or there are two types of mold copper plates with electroplated surfaces The surface joints are prone to technical problems with hard damage areas.
  • the present invention proposes the following technical solutions:
  • the mold copper plate includes an upper port and a lower port, including a copper substrate, a first plating layer and a second plating layer; the direction of connecting the lower port and the upper port is defined as the vertical direction;
  • the surface of the copper substrate on the side to be electroplated includes a first plane and a second plane, the first plane covers the upper mouth area, and the first plane is parallel to the vertical direction; the second plane covers the lower mouth area, And the second plane is an inclined plane, the upper end of the second plane is smoothly connected with the first plane, and the lower end of the second plane is inclined toward the inner side of the copper substrate with respect to the upper end of the second plane;
  • the first plating layer covers the surface of the copper substrate on the side to be electroplated; the outer surface of the first plating layer is parallel to the surface of the copper substrate where it is attached;
  • the second plating layer covers the second plane, and the outer surface of the second plating layer is parallel to the up and down direction, and in the transition area between the upper mouth and the lower mouth, the outer surface of the second plating layer and the outer surface of the first plating layer Smooth connections between surfaces.
  • the first plating layer is a nickel layer.
  • the second plating layer is a nickel alloy layer.
  • the invention also discloses the electroplating process of the above-mentioned crystallizer copper plate, which defines the connection direction of the lower port and the upper port of the crystallizer copper plate as the up and down direction, and the processing is performed according to the following method:
  • Step 1 Process the surface of the copper plate material on the side to be electroplated to obtain the copper substrate, including processing the upper mouth area into a first plane parallel to the up and down direction, and processing the lower mouth area to incline from top to bottom toward the inside of the copper plate The upper end of the second plane is smoothly connected to the first plane;
  • Step two electroplating the side of the copper substrate to be electroplated to form a nickel layer on the surface of the copper substrate;
  • Step 3 Process the side to be electroplated of the semi-finished product obtained in Step 2 to reduce the thickness of the nickel layer on the second plane;
  • Step 4 Electroplating the lower mouth area on the side to be electroplated of the semi-finished product obtained in step 3, so that a nickel alloy layer is formed in the lower mouth area;
  • Step 5 Process the surface of the electroplating side of the semi-finished product obtained in Step 4 so that the nickel alloy layer and the nickel layer are on the same plane and parallel to the up and down direction.
  • the electroplating bath during electroplating is a nickel-cobalt alloy bath, wherein:
  • the electroplating process parameters are:
  • the plating time is 60h ⁇ 80h.
  • the crystallizer copper plate prepared by the electroplating process of the above-mentioned crystallizer copper plate has a nickel layer at the upper mouth and good thermal deformation resistance, and a nickel alloy layer at the lower mouth and good wear resistance.
  • the nickel alloy layer is plated on the nickel layer, and the bonding force of the plating layer is good. After the joints between the plating layers are processed, the surface is smooth and no hard injury area is formed.
  • the technical solution of the present invention provides a mold copper plate and its electroplating process.
  • the mold copper plate has a two-layer plating structure, and the nickel layer covers the entire copper substrate, and the nickel alloy layer is arranged in the lower area.
  • the above-mentioned structure makes the bonding force of the plating layer good, and the performance of the plating layer is suitable for the surface performance requirements of different areas of the mold copper plate .
  • the joints between the plating layers have good bonding strength, smooth surface, and no hard damage area.
  • a special-shaped copper substrate is used and a layer of pure nickel with lower hardness is first electroplated on the surface of the copper substrate.
  • a layer of nickel-cobalt alloy with high hardness is electroplated on the surface of the nickel layer, which is retained on the mouth after processing
  • the nickel layer and the lower mouth retain the nickel-cobalt alloy layer, which solves the problem of heat resistance of the upper mouth of the mold copper plate and the wear resistance of the lower mouth, increases the number of steel furnaces of the mold copper plate, improves production efficiency and reduces costs.
  • Figure 1 is a schematic diagram of the structure of the copper plate of the mold in the present invention.
  • the present invention develops a new type of mold copper plate structure based on the upper and lower mouths of the mold copper plate that need to meet different performance requirements during use.
  • the upper and lower mouths are plated with different material coatings, and the coatings have good adhesion and can avoid A hard injury area appears at the transition between the two coatings.
  • a mold copper plate as shown in FIG. 1 includes an upper port and a lower port, wherein the upper port is located in the upper area in FIG. 1 and the lower port is located in the lower area in FIG. 1.
  • Figure 1 is a side cross-sectional view of the mold copper plate in use.
  • the mold copper plate has a composite structure, and includes a copper substrate 1, a first plating layer 2 and a second plating layer 3.
  • the right side of the mold copper plate is the side in contact with molten steel. Therefore, the surface of the copper substrate 1 on this side needs to be electroplated.
  • the surface of the copper substrate 1 on the side to be electroplated includes a first plane 2-1 and a second plane 2-2.
  • the first plane 2-1 covers the upper mouth area, and the first plane 2-1 is connected to the upper and lower sides.
  • the direction is parallel;
  • the second plane 2-2 covers the lower mouth area, and the second plane 2-2 is an inclined plane, the upper end of the second plane 2-2 is smoothly connected with the first plane 2-1, and the lower end of the second plane 2-2
  • the upper end of the second plane 2-2 is inclined toward the inner side of the copper substrate 1.
  • the copper substrate used in the above-mentioned solution is different from the traditional copper substrate with a full surface on the electroplating side.
  • the lower port area of the copper substrate in this solution is inclined to the inside of the copper substrate, in order to be able to plate two layers of plating in this area later, and Keep the upper and lower mouth surfaces as a large plane after integral molding.
  • the first plating layer 2 uniformly covers the surface of the copper substrate 1 to be electroplated, and the outer surface of the first plating layer 2 is parallel to the surface of the copper substrate where it is attached.
  • the first plating layer 2 fully covers the copper substrate. On the one hand, it serves as the upper plating layer to withstand higher thermal stress requirements, and the other serves as the base layer of the lower second plating layer 3.
  • the second plating layer 3 covers the second plane 2-2, and the outer surface of the second plating layer 3 is parallel to the up and down direction, in the transition area between the upper mouth and the lower mouth, the outer surface of the second plating layer 3 Smooth connection with the outer surface of the first plating layer 2.
  • a large plane is formed between the second plating layer 3 and the first plating layer 2 in the upper mouth area, and there is no more damage area at the connection.
  • the specific embodiment of the present invention also provides process parameters such as the thickness and material of the coating layer.
  • the thickness of the first plating layer 2 is 0.2 mm to 0.4 mm.
  • the thickness of the second plating layer 3 at the lower mouth is 1.0mm-1.4mm.
  • the above thickness can save raw materials as much as possible while meeting the requirements of surface performance.
  • the first plating layer 2 is a nickel layer. Pure nickel has the characteristics of good stability and high temperature resistance, and is suitable for the catchy area.
  • the second plating layer 3 is a nickel alloy layer.
  • Nickel alloys can be made of nickel-iron, nickel-cobalt and other materials.
  • the upper mouth is a thinner first plating layer 2
  • the lower mouth is a composite layer of the first plating layer 2 and the thicker second plating layer 3, so that both the upper mouth and the lower mouth can simultaneously satisfy the use of mold copper plates Requirements.
  • the second plating layer 3 in the lower mouth area is closer to the lower mouth, the thickness of the plating layer becomes later, and the lower mouth area has the highest wear resistance.
  • the surface at the junction of the second plating layer 3 and the first plating layer 2 in the upper mouth area is smooth, and there are hardened areas on the wall surface.
  • Another embodiment of the present invention discloses an electroplating process of a mold copper plate, defining the connection direction of the lower port and the upper port of the mold copper plate as the up-down direction, and processing according to the following method:
  • Step 1 Process the surface of the copper plate raw material on the side to be electroplated to obtain the copper substrate 1, including processing the upper mouth area into a first plane 2-1 parallel to the up and down direction, and processing the lower mouth area from top to bottom A second plane 2-2 inclined toward the inside of the copper plate, and the upper end of the second plane 2-2 is smoothly connected with the first plane 2-1.
  • the overall height of the mold copper plate is 1200mm, and the height L1 of the upper mouth area is about 300mm , The height L2 of the lower mouth area is about 900mm.
  • the inclination angle of the second plane can be calculated according to the thickness of the plating layer and the size of the product, thereby processing the copper substrate 1.
  • Step two electroplating the side of the copper substrate 1 to be electroplated to form a nickel layer on the surface of the copper substrate 1. Since the surface of the electroplating process is not completely flat, it is necessary that the thickness of the nickel layer is thicker than the thickness of the first plating layer in the final finished state, leaving some margin so that further surface treatment can be performed later. It is recommended that the thickness of the nickel layer here is greater than or equal to 0.4mm.
  • the electroplating process here is a common nickel electroplating process. Specifically, in this embodiment, nickel is electroplated in a sulfamate bath, the concentration of nickel sulfamate is 400g/L-600g/L, and the current density is 2A/dm 2 -4A/dm 2 , the plating time is 40 hours to 60 hours.
  • Step 3 Process the side to be electroplated of the semi-finished product obtained in Step 2 to reduce the thickness of the nickel layer on the second plane 2-2.
  • the thickness of the nickel layer is reduced to 0.2 mm to 0.4 mm, preferably 0.3 mm.
  • machine tool processing can be selected to make the surface of the nickel layer on the second plane 2-2 uniform as the base layer of the second plating layer 3, so that the second plating layer 3 has excellent bonding force.
  • Step 4 Electroplating the lower mouth area of the side to be electroplated of the semi-finished product obtained in step 3, so that a nickel alloy layer is formed in the lower mouth area, and the thickness of the nickel alloy layer is greater than or equal to 1.0 mm.
  • the concentration of cobalt sulfamate in the nickel-cobalt alloy solution can be selected to be higher, which is conducive to the formation of better wear resistance.
  • the upper mouth area is appropriately shielded or the height of the upper surface of the plating solution is reduced, so that it is located at the uppermost end of the second plane 2-2 or slightly higher than the uppermost end of the second plane 2-2.
  • Step 5 Process the surface of the electroplating side of the semi-finished product obtained in Step 4 so that the nickel alloy layer and the nickel layer are on the same plane and parallel to the up and down direction.
  • the remaining amount of the first plating layer 2 in the upper mouth area is also processed to obtain a smooth surface.
  • the thickness of the nickel layer on the first plane 2-1 is 0.2 mm to 0.4 mm.
  • the thickness of the nickel alloy layer is 1.0 mm to 1.4 mm remaining at the lowermost position. In some specific embodiments, it is preferable to retain the 0.3mm nickel layer and the 1.2mm nickel alloy layer at the lowermost position, which is sufficient to meet the thermal deformation and wear resistance requirements of the mold copper plate in use.
  • the electroplating bath during electroplating is a nickel-cobalt alloy bath, which is:
  • the electroplating process parameters are:
  • the plating time is 60h ⁇ 80h.
  • Nickel solution in which the concentration of nickel sulfamate is 500g/L, the concentration of nickel chloride is 12g/L, and the concentration of boric acid is 30g/L;
  • Nickel-cobalt alloy solution in which the concentration of nickel sulfamate is 600g/L, the concentration of cobalt sulfamate is 30g/L, the concentration of nickel chloride is 12g/L, and the concentration of boric acid is 30g/L;
  • the first step processing the copper plate
  • Step 2 Electroplating the nickel layer
  • Electroplating is carried out in a nickel solution, the bath temperature is 52°C, the current density is 3A/dm 2 , and the electroplating time is 48 hours.
  • the specific process is as follows:
  • the surface of the copper plate is activated by pickling with phosphoric acid. After activation, the water film on the surface of the copper plate is guaranteed to be completed, and the pH value is 7;
  • the third step nickel plating layer processing
  • the fourth step nickel-cobalt alloy plating on the surface of the mold copper plate
  • Electroplating is carried out in a nickel-cobalt alloy solution, the bath temperature is 52°C, the current density is 3A/dm 2 , and the electroplating time is 72 hours.
  • the specific process is as follows:
  • the surface of the copper plate is activated by pickling with phosphoric acid. After activation, the water film on the surface of the copper plate is guaranteed to be completed, and the pH value is 7;
  • the fourth step the finished copper plate processing of the mold
  • the above process is electroplated twice on the surface of the mold copper plate. First, a layer of pure nickel is electroplated, and then a layer of nickel-cobalt alloy is electroplated after processing. After the layered plating is completed, the mold copper plate is formed. The physical properties of the copper plate surface are tested, the hardness and The bonding force has reached the requirements. After the mold copper plate is used on the line, the upper mouth has good heat resistance and lower mouth wear resistance, and there is no hard zone at the transition between the upper mouth and the lower mouth, which fully meets the production requirements.

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Abstract

一种结晶器铜板及其分层电镀工艺，采取异形铜基板(1)并先在铜基板(1)表面电镀一层硬度较低的纯镍，处理后在镍层表面电镀一层硬度高的镍钴合金，经过加工后上口保留镍层，下口保留镍钴合金层，这样解决结晶器铜板上口抗热变性问题和下口的耐磨问题，提高结晶器铜板的通钢炉数，提高生产效率，降低成本。

Description

结晶器铜板及其分层电镀工艺 技术领域
本发明涉及电镀技术领域，特别是结晶器铜板的电镀技术。
背景技术
结晶器铜板用于钢铁冶金中的连铸机上，是连铸的核心部件，结晶器铜板作为连铸从液态钢水到凝固成固态坯壳的重要导热部件，其质量好坏直接影响到铸坯的表面质量、连铸机拉速等指标。熔融的钢水流经结晶器铜板，在外界冷却水的作用下结晶成钢坯，并被引锭杆从结晶器中拉出。
上述过程中，钢水在结晶器铜板的上口是呈液态，到下口后表面形成一层坯壳，在这种工作状态下造成了结晶器铜板的上口承受着钢水的高温，下口承受着钢坯的磨损。而连铸机在工作时要求单次通钢量高、拉速快，因此对结晶器铜板的表面质量要求非常高。其中，结晶器铜板上口镀层在高温状况下要求有稳定的抗热变性，结晶器铜板下口镀层在钢坯的磨损下要求有良好的耐磨性。因此一般结晶器铜板镀层要求上口硬度偏低用于抗热变，下口硬度高用于耐磨。
目前常见的结晶器铜板表面采用单一镀层，铜板表面整体电镀一层镍、镍铁、镍钴、钴镍等镀层，这样的镀层不能兼顾上口的低硬度和下口的高硬度要求，在未达到理想的通钢炉数后会出现下口磨损量大或上口出现热裂纹甚至镀层脱落情况。
本领域技术人员为了提高结晶器铜板表面的性能，陆续开发了新工艺。
例如，专利申请号为201210269246.X的专利公开了一种高拉速连铸机结晶器铜板电镀工艺，通过对结晶器铜板表面采用不同的电镀液进行分别电镀，获得了上口和下口不同的表面性能，其中上表面为耐高温镀层，下表面为抗磨镀层。该方案的出发点在于针对电镀液进行了调配，分别两头电镀获得不同的表面，从而解决了上述问题。但上述方案会导致镀层结合面上是两种结构，容易 在两种结构的连接处形成硬伤区，出现龟裂和剥落。
又如，专利申请号为201210269259.7的专利公开了一种结晶器铜板上下镀层一次电镀成型电解槽，希望通过电解槽的结构一次性解决前一专利方法中提到的需要两次电镀的问题。但是该专利中的结晶器铜板在电镀时与实际使用时的上口、下口方向不一致，导致电镀出来的表面不符合实际使用需求；并且电解槽中使用的薄膜会使得结晶器铜板表面相应的位置无法电镀上，从而存在一条缝隙，影响结晶器铜板表面质量。
因此，上述两次电镀的方案无论是采用哪种形式均无法获得良好的表面质量。
发明内容
本发明目的在于提供一种结晶器铜板，该结晶器铜板采用新的电镀工艺，解决了传统的一致的结晶器铜板表面上下口性能无法适应不同的要求，或者存在两种电镀表面的结晶器铜板表面连接处容易出现硬伤区的技术问题。
为达成上述目的，本发明提出如下技术方案：
结晶器铜板，包括上口和下口，包括铜基板、第一镀层和第二镀层；定义下口与上口连线所在的方向为上下方向；
所述铜基板的待电镀一侧的表面包括第一平面和第二平面，所述第一平面覆盖在上口区域，且第一平面与上下方向平行；所述第二平面覆盖在下口区域，且第二平面为斜面，第二平面上端与第一平面平滑连接，第二平面下端相对于第二平面的上端向铜基板内侧倾斜；
所述第一镀层覆盖于铜基板的待电镀一侧的表面上；第一镀层的外表面与其附着处的铜基板表面平行；
所述第二镀层覆盖在第二平面上，且第二镀层的外表面与上下方向平行，在上口和下口之间的过渡区域，所述第二镀层的外表面与第一镀层的外表面之间平滑连接。
进一步的，在本发明中，所述第一镀层为镍层。
进一步的，在本发明中，所述第二镀层为镍合金层。
本发明同时还公开了上述结晶器铜板的电镀工艺，定义结晶器铜板的下口与上口连线所在的方向为上下方向，按照以下方法进行加工：
步骤一、对铜板原料的待电镀一侧的表面进行加工以获得铜基板，包括将上口区域加工成平行于上下方向的第一平面，将下口区域加工成自上向下朝向铜板内部倾斜的第二平面，且第二平面上端与第一平面平滑连接；
步骤二、将铜基板的待电镀一侧进行电镀，在铜基板表面形成一层镍层；
步骤三、将步骤二中获得的半成品的待电镀一侧进行加工，使第二平面上的镍层厚度减小；
步骤四、将步骤三中获得的半成品的待电镀一侧的下口区域进行电镀，使得下口区域形成一层镍合金层；
步骤五、将步骤四中获得的半成品的电镀一侧的表面进行加工，使得镍合金层与镍层在同一平面上且均平行于上下方向。
进一步的，在本发明中，所述步骤四中，电镀时的电镀液为镍钴合金渡液，其中：
氨基磺酸镍浓度：450g～700g/L；
氨基磺酸钴浓度：15g～35g/L；
电镀工艺参数为：
电流密度：2.5A～5A/dm 2；
电镀时间60h～80h。
通过上述结晶器铜板的电镀工艺制备的结晶器铜板，上口为镍层，抗热变性能好，下口为镍合金层，耐磨性能好。并且镍合金层镀在镍层之上，镀层的结合力好，镀层之间的连接处经加工后，表面平整，不会形成硬伤区。
有益效果：
由以上技术方案可知，本发明的技术方案提供了一种结晶器铜板及其电镀工艺。
该结晶器铜板具有两层镀层结构，并且镍层布满整个铜基板，镍合金层布置在下区域，上述结构使得镀层的结合力好，且镀层的性能适合结晶器铜板不同区域对表面性能的要求。同时，镀层之间的结合处，结合力好，表面平整，不会产生硬伤区。
上述结晶器铜板在制备时，采取异形铜基板并先在铜基板表面电镀一层硬度较低的纯镍，处理后在镍层表面电镀一层硬度高的镍钴合金，经过加工后上口保留镍层，下口保留镍钴合金层，这样解决结晶器铜板上口抗热变性问题和下口的耐磨问题，提高结晶器铜板的通钢炉数，提高生产效率，降低成本。
应当理解，前述构思以及在下面更加详细地描述的额外构思的所有组合只要在这样的构思不相互矛盾的情况下都可以被视为本公开的发明主题的一部分。
结合附图从下面的描述中可以更加全面地理解本发明教导的前述和其他方面、实施例和特征。本发明的其他附加方面例如示例性实施方式的特征和/或有益效果将在下面的描述中显见，或通过根据本发明教导的具体实施方式的实践中得知。
附图说明
附图不意在按比例绘制。在附图中，在各个图中示出的每个相同或近似相同的组成部分可以用相同的标号表示。为了清晰起见，在每个图中，并非每个组成部分均被标记。现在，将通过例子并参考附图来描述本发明的各个方面的实施例，其中：
图1为本发明中结晶器铜板的结构示意图。
图中，各附图标记的含义如下：
1、铜基板；2、第一镀层；2-1、第一平面；2-2、第二平面；3、第二镀层。
具体实施方式
为了更了解本发明的技术内容，特举具体实施例并配合所附图式说明如下。
在本公开中参照附图来描述本发明的各方面，附图中示出了许多说明的实施例。本公开的实施例不必定意在包括本发明的所有方面。应当理解，上面介绍的多种构思和实施例，以及下面更加详细地描述的那些构思和实施方式可以以很多方式中任意一种来实施，这是因为本发明所公开的构思和实施例并不限于任何实施方式。另外，本发明公开的一些方面可以单独使用，或者与本发明公开的其他方面的任何适当组合来使用。
本发明基于结晶器铜板的上下口在使用时需要满足不同的性能的要求出发，研发了一种新型的结晶器铜板结构，上下口镀不同的材质的镀层，且镀层的结合力好，能避免两种镀层过渡处出现硬伤区。
如图1所示的一种结晶器铜板，包括上口和下口，其中上口位于图1中的上方区域，下口位于图1中的下方区域。
图1为结晶器铜板使用状态下的侧面剖视图，为了说明的方便，定义下口与上口连线所在的方向为上下方向。该结晶器铜板为复合结构，包括铜基板1、第一镀层2和第二镀层3。
图中，结晶器铜板的右侧为与钢水接触的一侧，因此，该侧的铜基板1的表面需要电镀。
所述铜基板1的待电镀一侧的表面包括第一平面2-1和第二平面2-2，所述第一平面2-1覆盖在上口区域，且第一平面2-1与上下方向平行；所述第二平面2-2覆盖在下口区域，且第二平面2-2为斜面，第二平面2-2上端与第一平面2-1平滑连接，第二平面2-2下端相对于第二平面2-2的上端向铜基板1内侧倾斜。
上述方案中采用的铜基板与传统的带电镀一侧为整面平面的铜基板不同，本方案的铜基板的下口区域向铜基板内部倾斜，为了后期在该区域能够镀两层镀层，且保持整体成型后上下口表面为一个大平面。
在铜基板表面，所述第一镀层2均匀覆盖于铜基板1的待电镀一侧的表面上，第一镀层2的外表面与其附着处的铜基板表面平行。第一镀层2全面覆盖铜基板，一方面作为上口的镀层以承受较高的热应力要求，另一方作为下口第 二镀层3的基层。
所述第二镀层3覆盖在第二平面2-2上，且第二镀层3的外表面与上下方向平行，在上口和下口之间的过渡区域，所述第二镀层3的外表面与第一镀层2的外表面之间平滑连接。第二镀层3与上口区域的第一镀层2之间形成一个大平面，连接处不再有硬伤区存在。
更进一步的，为了获得较好的表面质量，本发明的具体实施例还提供了镀层厚度、材质等工艺参数。具体的，
由于第一镀层2主要起到耐高温的作用，因此，所述第一镀层2厚度为0.2mm～0.4mm。
由于第二镀层3主要起到耐磨的作用，尤其以最下口的区域最甚，因此，所述第二镀层3在下口处的厚度为1.0mm～1.4mm。
上述厚度在满足表面性能的要求下可以尽可能地节省原料。
在本实施例中，所述第一镀层2为镍层。纯镍具有稳定性好、耐高温的特点，适合用于上口的区域。
在本实施例中，所述第二镀层3为镍合金层。镍合金可以采用镍铁、镍钴等材质。
本发明的具体实施例上口为较薄的第一镀层2，下口为第一镀层2和较厚的第二镀层3的复合层，使得上口和下口均能同时满足结晶器铜板使用的要求。并且下口区域的第二镀层3随着越靠近下口，镀层厚度越后，在最下口的区域具有最高的耐磨性能。在第二镀层3与上口区域的第一镀层2结合处表面平整，壁面出现硬伤区域。
本发明的另一个实施例公开一种结晶器铜板的电镀工艺，定义结晶器铜板的下口与上口连线所在的方向为上下方向，按照以下方法进行加工：
步骤一、对铜板原料的待电镀一侧的表面进行加工以获得铜基板1，包括将上口区域加工成平行于上下方向的第一平面2-1，将下口区域加工成自上向下朝向铜板内部倾斜的第二平面2-2，且第二平面2-2上端与第一平面2-1平滑连接。
由于上口区域和下口区域的区分为本领域技术人员的公知常识，例如，图1中所示出的方案，该结晶器铜板的整体高度为1200mm，其中上口区域的高度L1约为300mm，下口区域的高度L2约为900mm。
划分好上口区域和下口区域后，根据镀层的厚度以及产品的尺寸可以计算出第二平面的倾斜角度，由此进行加工铜基板1。
步骤二、将铜基板1的待电镀一侧进行电镀，在铜基板1表面形成一层镍层。由于电镀工艺表面并非完全平整的表面，因此需要此时镍层的厚度比最终的成品状态时第一镀层的厚度更厚一些，留有一些余量，以便后期可以进一步进行表面处理。建议此处镍层厚度大于等于0.4mm。
此处的电镀工艺为常见的电镀镍工艺，具体的，在本实施例中，在氨基磺酸盐的镀液内电镀镍，氨基磺酸镍浓度为400g/L-600g/L，电流密度为2A/dm 2-4A/dm 2，电镀时间为40小时-60小时。
步骤三、将步骤二中获得的半成品的待电镀一侧进行加工，使第二平面2-2上的镍层厚度减小。镍层厚度减小为0.2mm～0.4mm，优选0.3mm。此处可选择机床加工，使得第二平面2-2上的镍层表面均匀以作为第二镀层3的基层，使得第二镀层3具有优良的结合力。
步骤四、将步骤三中获得的半成品的待电镀一侧的下口区域进行电镀，使得下口区域形成一层镍合金层，镍合金层的厚度大于等于1.0mm。镍钴合金溶液中的氨基磺酸钴浓度可以选择浓度较高一些，有利于形成较好的耐磨性能。此时，对上口区域进行适当的遮挡或者选择降低镀液上表面的高度，使得位于第二平面2-2的最上端或略高于第二平面2-2的最上端。当然也可以选择对上口区域进行同时电镀，但考虑到节约成本，此处建议对上口区域不进行电镀。
步骤五、将步骤四中获得的半成品的电镀一侧的表面进行加工，使得镍合金层与镍层在同一平面上且均平行于上下方向。这里可以选择车床加工，将电镀一层整体切削掉一部分形成统一平整的表面，此时还同时将上口区域第一镀层2的余量给处理掉，从而获得了平滑的表面。
所述步骤五中，第一平面2-1上的镍层的厚度为0.2mm～0.4mm。镍合金层的厚度为在最下口的位置保留1.0mm～1.4mm。在某些具体的实施例中，优选保留0.3mm镍层和最下口的位置保留1.2mm的镍合金层，足以应对结晶器铜板使用时的抗热变形要求和耐磨性要求。
在某些具体的实施例中，所述的结晶器铜板的电镀工艺，所述步骤四中，电镀时的电镀液为镍钴合金渡液，其中为：
氨基磺酸镍浓度：450g～700g/L；
氨基磺酸钴浓度：15g～35g/L；
电镀工艺参数为：
电流密度：2.5A～5A/dm 2；
电镀时间60h～80h。
具体实施例1
原料：
铜板，长度为1200mm；上方L1＝300mm为上口区域，下方L2＝900mm为下口区域；
镍溶液，其中，氨基磺酸镍浓度500g/L，氯化镍浓度12g/L，硼酸浓度30g/L；
镍钴合金溶液，其中，氨基磺酸镍浓度600g/L，氨基磺酸钴浓度30g/L，氯化镍浓度12g/L，硼酸浓度30g/L；
加工过程：
第一步：加工铜板
将铜板放置于工装上进行车削加工，将铜板下口区域加工成图1中所示的倾斜面，倾斜角度约为arctan750；
第二步：电镀镍层
在镍溶液中进行电镀，镀液温度为52℃，电流密度为3A/dm 2，电镀时间为48小时。具体过程如下：
1、将铜板安装到电镀工装上，非电镀面进行遮蔽，铜板表面用碱清洗剂清洗干净，保证表面水膜完整；
2、铜板表面用磷酸进行酸洗活化，活化后保证铜板表面水膜完成，PH值为7；
3、将铜板周边用PVC板进行遮蔽；
4、铜板下镀槽，下槽后连接电源，将电流调至要求值(根据铜板表面积和电流密度计算得出电流值)。
5、48小时后铜板出槽，将铜板表面冲洗干净，拆除所有遮蔽板。
第三步：镀镍层加工
1、用螺栓将结晶器铜板连接到专用加工工装上，然后整体固定在机床工作台上，用百分表进行找正，确保工件的直线度和平面度；
2、将铜板表面镍镀层按图纸要求进行加工，下口保留0.3mm的镍层。
第四步：结晶器铜板表面镀镍钴合金
在镍钴合金溶液中进行电镀，镀液温度为52℃，电流密度为3A/dm 2，电镀时间为72小时。具体过程如下：
1、将铜板安装到电镀工装上，非电镀面进行遮蔽，铜板表面用碱清洗剂清洗干净，保证表面水膜完整；
2、铜板表面用磷酸进行酸洗活化，活化后保证铜板表面水膜完成，PH值为7；
3、将铜板周边用PVC板进行遮蔽，上口0～300mm进行遮挡；
4、铜板下镀槽，下槽后连接电源，将电流调至要求值(根据铜板表面积和电流密度计算得出电流值)；
5、72小时后铜板出槽，将铜板表面冲洗干净，拆除所有遮蔽板。
第四步：结晶器铜板成品加工
1、用螺栓将结晶器铜板连接到专用加工工装上，然后整体固定在机床工作台上，用百分表进行找正，确保工件的直线度和平面度；
2、将结晶器铜板按图纸要求进行加工，加工后保证上口0～300mm有0.3mm的镍层，300mm以下镀层厚度逐渐增加，下口边缘保证1.5mm的镀层。
上述工艺对结晶器铜板表面进行两次电镀，先电镀一层纯镍，加工后再电镀一层镍钴合金，分层电镀结束后形成结晶器铜板，对铜板表面的物理性能进行测试，硬度和结合力都达到了要求，该结晶器铜板在上线使用后上口的抗热变性、下口耐磨性较好，并且上口和下口过渡处无硬伤区，完全符合生产要求。
虽然本发明已以较佳实施例揭露如上，然其并非用以限定本发明。本发明所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作各种的更动与润饰。因此，本发明的保护范围当视权利要求书所界定者为准。

Claims (12)

  1. 结晶器铜板，包括上口和下口，其特征在于：包括铜基板、第一镀层和第二镀层；定义下口与上口连线所在的方向为上下方向；
    所述铜基板的待电镀一侧的表面包括第一平面和第二平面，所述第一平面覆盖在上口区域，且第一平面与上下方向平行；所述第二平面覆盖在下口区域，且第二平面为斜面，第二平面上端与第一平面平滑连接，第二平面下端相对于第二平面的上端向铜基板内侧倾斜；
    所述第一镀层覆盖于铜基板的待电镀一侧的表面上；第一镀层的外表面与其附着处的铜基板表面平行；
    所述第二镀层覆盖在第二平面上，且第二镀层的外表面与上下方向平行，在上口和下口之间的过渡区域，所述第二镀层的外表面与第一镀层的外表面之间平滑连接。
  2. 根据权利要求1所述的结晶器铜板，其特征在于：所述第一镀层厚度为0.2mm～0.4mm。
  3. 根据权利要求2所述的结晶器铜板，其特征在于：所述第二镀层在下口处的厚度为1.0mm～1.4mm。
  4. 根据权利要求1所述的结晶器铜板，其特征在于：所述第一镀层为镍层。
  5. 根据权利要求4所述的结晶器铜板，其特征在于：所述第二镀层为镍合金层。
  6. 结晶器铜板的电镀工艺，其特征在于：定义结晶器铜板的下口与上口连线所在的方向为上下方向，按照以下方法进行加工：
    步骤一、对铜板原料的待电镀一侧的表面进行加工以获得铜基板，包括将上口区域加工成平行于上下方向的第一平面，将下口区域加工成自上向下朝向铜板内部倾斜的第二平面，且第二平面上端与第一平面平滑连接；
    步骤二、将铜基板的待电镀一侧进行电镀，在铜基板表面形成一层镍层；
    步骤三、将步骤二中获得的半成品的待电镀一侧进行加工，使第二平面上 的镍层厚度减小；
    步骤四、将步骤三中获得的半成品的待电镀一侧的下口区域进行电镀，使得下口区域形成一层镍合金层；
    步骤五、将步骤四中获得的半成品的电镀一侧的表面进行加工，使得镍合金层与镍层在同一平面上且均平行于上下方向。
  7. 根据权利要求6所述的结晶器铜板的电镀工艺，其特征在于：所述步骤二中，镍层厚度大于等于0.4mm。
  8. 根据权利要求6所述的结晶器铜板的电镀工艺，其特征在于：所述步骤三中，镍层厚度减小为0.2mm～0.4mm。
  9. 根据权利要求6所述的结晶器铜板的电镀工艺，其特征在于：所述步骤四中，镍合金层的厚度大于等于1.0mm。
  10. 根据权利要求6所述的结晶器铜板的电镀工艺，其特征在于：所述步骤五中，第一平面上的镍层的厚度为0.2mm～0.4mm。
  11. 根据权利要求6所述的结晶器铜板的电镀工艺，其特征在于：所述步骤四中，电镀时的电镀液为镍钴合金渡液，其中：
    氨基磺酸镍浓度：450g～700g/L；
    氨基磺酸钴浓度：15g～35g/L；
    电镀工艺参数为：
    电流密度：2.5A～5A/dm 2；
    电镀时间60h～80h。
  12. 一种通过权利要求6-11中任意一项所述的结晶器铜板的电镀工艺制备的结晶器铜板。
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CN114043190A (zh) * 2021-11-09 2022-02-15 攀钢集团工程技术有限公司 一种板坯连铸机结晶器宽面铜板的装配方法

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