WO2003064077A1

WO2003064077A1 - Mold copper sheet for continuous casting manufacturing same

Info

Publication number: WO2003064077A1
Application number: PCT/JP2003/000778
Authority: WO
Inventors: Seiji Itoyama; Yukio Inokuti; Tetsuya Fujii; Masaharu Oishi
Original assignee: Jfe Steel Corporation
Priority date: 2002-01-29
Filing date: 2003-01-28
Publication date: 2003-08-07
Also published as: KR100623012B1; KR20040073594A; CN1285431C; CN1625450A

Abstract

[PROBLEM] To provide a mold copper sheet for continuous casting having a high adhesion to the mold copper sheet base even when it is actually used for continuous casting and comprising a surface coating layer excellent in wear resistance. [MEANS FOR SOLVING THE PROBLEM] A metal layer of one or more kinds of metals selected from Ti, Cr, Ni, B, Si, and Al is formed as the innermost layer on the surface of a mold copper sheet base. Layers of a nitride or carbide of the metals of the metal layer or of a carbonitride and layers of the metals are alternated on the metal layer. A nitride, carbide, or carbonitride layer is formed as the outermost layer. The layers are preferably formed by PVD. At least the metal layer, the innermost layer, is desirably formed by using a bias voltage of the arc cut.

Description

Specification

Monoredo copper plate for continuous production and its manufacturing method Technology

TECHNICAL FIELD The present invention relates to a copper plate suitable for use as a metal component used for continuous production of molten metal, particularly molten steel, and particularly suitable as a molded copper plate for producing molten metal. The present invention also relates to a technique for advantageously improving the durability of the molded copper sheet or a technique for enabling strong cooling.

The present invention also relates to a method for producing the above-described molded copper sheet for continuous production. In particular, the present invention relates to a manufacturing technique for effectively improving the adhesiveness of a wear-resistant coating layer formed on the surface of a molded copper plate to further improve the durability of the molded copper plate. Background art

In recent years, in continuous production of molten metal, especially molten steel, productivity has been improved by increasing the production speed. At the same time, it is also required to efficiently produce pieces of various types and sizes.

Generally, for continuous production of molten metal, a water-cooled mold whose upstream and downstream sides in the production direction are open is used. That is, a method is employed in which a molten metal is poured into the mold, and the molten metal is solidified by removing heat from the molten metal to the other side, and a piece produced in the downstream direction is pulled out. At this time, the mold repetitively vibrates along the fixed force or the construction direction. However, friction is generated between the piece and the mold regardless of the shape of the mold. In addition, the surface that comes into contact with the piece of m is constantly exposed to high temperatures, so it receives a large heat load, especially on its surface. Of course, mold flux containing oxide as a main component is used for lubrication between mold / piece, heat retention of molten metal surface and oxidation prevention. However, particularly in the case of a high-speed continuous structure, the relative speed with respect to the piece increases, so that the frictional force applied to the mold increases significantly. Moreover, since the temperature inside the mold increases due to the increase in speed, the heat load applied to the mold is significantly increased. As a result, cracks easily occur on the surface as the number of uses increases. Also, in continuous slab fabrication, the slab width is often changed during fabrication in order to perform efficient fabrication. Also in this case, a remarkably large frictional force is generated between the ^ M and the piece as compared with the insertion in the steady state.

Furthermore, when performing continuous production of high-grade steel such as stainless steel or high carbon steel with high hot strength, the surface wear becomes remarkable because the hardness of the solidified shell is higher than that of ordinary steel. . Therefore, various researches and developments have been made in order to improve the durability of type III.

Usually, a copper plate (hereinafter, referred to as a molded copper plate) is disposed as a component on the side in contact with the piece in order to increase the cooling efficiency of the piece. Precipitated and hardened copper alloy material is mainly used for the current molded copper sheet in order to extend the life of the copper sheet and secure the material strength to withstand high temperatures.

Further, the surface of the molded copper plate is generally coated with an alloy such as Ni-I, Fe-Ni, Co-Ni by a wet plating method or a thermal spraying method.

However, even if the substrate surface of the above-mentioned precipitation hardening type copper alloy material is coated by wet plating or thermal spraying as described above, a molded copper plate (surface treatment material) can be made of stainless steel or high carbon steel. The service life when used for continuous production of steel was similar to or shorter than that used for continuous production of ordinary steel. Therefore, in order to extend the life of a molded copper plate used for continuous production of high-strength steel such as stainless steel and high carbon steel, it is essential to cleave a new mold surface treatment material.

From this point of view, JP-A-9-1314288 discloses that the surface of a molded copper plate is made of metal (Al, group 4A element (Ti, Zr, etc.), group 5A element (V, b, Ta, etc.), group 6A element ( It is proposed to coat with nitrides of Cr, Mo, etc.) and Fe). This is because such nitrides have extremely high hardness, so that the wear resistance of the molded copper plate can be expected to be improved.

In addition, since such nitride coating debris has poor adhesion to the mold copper plate base material, the gazette preferably discloses an alloy such as an Fe alloy, a Ni alloy, and a Co alloy as a base layer of the nitride coating. It is recommended that plating be applied. Disclosure of the invention

[Problems to be solved by the invention]

In the above-mentioned Japanese Patent Application Laid-Open No. 9-314288, it has been reported that good results were obtained in crack resistance and abrasion resistance by laboratory tests.

However, when the present inventors used the continuous machine in an actual continuous structure, cracks were generated in the coated nitride layer, and the nitride layer peeled off when severe lifting occurred, resulting in a long period of time. It turned out that continuous use of was not possible. In addition, ceramic layers such as nitrides may deteriorate the effect of heat extraction from the molten metal by the copper plate.

Honkiaki has been developed in view of the above situation, and has a surface coating layer that has high adhesion to the mold copper plate base, excellent wear resistance, and high heat removal effect even in actual use. It is an object of the present invention to propose a mold copper plate for continuous production having an advantageous manufacturing method. Honoki also further improved the above-mentioned technology to increase the density of the wear-resistant coating layer on the molded copper plate. An object of the present invention is to propose an advantageous method for producing a molded copper plate for continuous production, in which the adhesion is further improved and the durability and the like of the molded copper plate are further improved.

[Means for solving the problem]

In order to achieve the above-mentioned object, the inventors of the present invention have proposed how to form carbides and nitrides of various metals having high hardness and excellent wear resistance on a copper or copper alloy substrate in an actual continuous structure. Intensive study was conducted to determine whether or not the adhesive should be firmly adhered so as not to cause peeling or cracking even after long-term use in the environment.

As a result, using a dry plating method, especially a PVD (Physical Vapor Deposition) method that is excellent in ionization rate and capable of high-speed film formation, particularly preferably an HCD (Hollow Cathode Discharge) method or an arc discharge method,

(1) By forming a metal layer composed of one or more metals selected from Ti, Cr, Ni, B, Si and Al as the innermost layer of the wear-resistant coating on the surface of the molded copper plate , Strong adhesion to copper plate is ensured,

(2) As the outermost layer of the abrasion-resistant coating, the metal group (Ti, Cr, Ni, B, Si and Al) is selected from one or more selected nitrides or carbides (carbon nitrides). System, the same applies hereinafter), it is possible to secure not only high strength, but also excellent wear resistance and heat resistance, and also to ensure the heat removal effect.

(3) Further, between the innermost layer and the outermost layer, a ceramic layer made of nitride or carbide of one or more metals selected from the metal group, and one or more selected from the metal group By alternately laminating metal layers composed of two or more metals, the internal strain of the abrasion-resistant composite coating is effectively alleviated and not only the adhesion to the copper plate is further improved, but also the abrasion resistance is improved. Exfoliation of wear-resistant composite coatings. Cracking in the composite coating, especially in the ceramic coating Life can be effectively prevented.

I found that new.

The present invention is based on the above findings.

That is, the gist of the present invention is as follows.

1. In a mold copper plate for continuous production of molten metal, the innermost layer was selected from the group of metals Ti, Cr, Ni, B, Si and Al on the surface of the copper or copper alloy plate as the base material. A metal layer composed of one or more metals is provided, on which a nitride or carbide layer of one or more metals selected from the metal group and one or two layers selected from the metal group One or more sets of layers made of the above metals are stacked alternately, and a nitride or carbide layer of one or more metals selected from the above metal group is provided as the outermost layer. Molded copper plate for continuous production.

2. The mold copper plate for continuous production according to the above 1, wherein a mixed layer of a metal of the innermost layer and a metal constituting the substrate is formed at a boundary between the innermost layer and the substrate.

3. The copper or copper alloy plate material as the base material is one whose surface is previously coated with one or two or more selected from Ni, Cr, Fe and Co. 3. The mold copper plate for continuous production according to the above item 1 or 2, characterized in that:

4. One or more metals selected from the group consisting of Ti, Cr, Ni, B, Si and Al as the innermost layer by the PVD method on the surface of the copper or copper alloy plate as the base material. A metal layer composed of one or two or more metals selected from the metal group, and a nitride or carbide layer of one or more metals selected from the metal group, and one or two or more metals selected from the metal group One or more layers of layers are alternately laminated, and a layer of a nitride or carbide of one or more metals selected from the metal group is further formed as an outermost layer; Plate manufacturing method. 5. The method for producing a mold copper plate for continuous ft forming according to the above item 4, wherein the method of forming the innermost layer is a high peer discharge coating method.

6. The plate material made of copper or copper alloy as the base material is characterized in that its surface is coated with one or more selected from Ni, Cr, Fe and Co as main components. 6. The method for producing a molded copper plate for continuous production according to the above item 4 or 5.

In the above description, "nitride or carbide" includes carbon nitride.

7. One or more metals selected from the group consisting of Ti, Cr, Ni, B, Si and Al as the innermost layer by the PVD method on the surface of copper or copper alloy plate material as the base material. A metal layer consisting of one or more metal nitrides, carbides or carbonitrides selected from the metal group, and one or more metal layers selected from the metal group One or more pairs of metal layers are alternately laminated, and a layer of a nitride, carbide, or carbon nitride of one or more metals selected from the above metal group is formed as the outermost layer. In the method of manufacturing a molded board,

A method for producing a mold copper sheet for continuous production, characterized in that at least the innermost metal layer is formed using a bias voltage of an arc cutter.

8. The copper or copper alloy plate material used as the base material shall be one whose surface has been previously coated with one or two selected from Ni, Cr, Fe and Co. The method for producing a molded copper sheet for continuous production according to the above-mentioned item 1, which is characterized in that:

In the above 1 to 8, each metal layer does not need to be composed of the same metal, and if one or two or more selected from Ti, Cr, Ni, B, Si and Al Different metals may be used. Similarly, each layer made of carbide, nitride or carbonitride need not be made of the same compound. Brief description of the drawings ''

FIG. 1A is a schematic sectional view of a surface-coated molded copper plate of the present invention.

FIG. 1B is a schematic cross-sectional view of a current surface-coated molded copper plate.

FIG. 2 is a diagram showing a comparison between the hardness of the surface-coated copper sheet of the present invention and the hardness of the existing surface-coated copper sheet.

FIG. 2B is a diagram showing a comparison of the adhesion between the surface-coated molded copper plate of the present invention and the existing surface-coated molded copper plate.

FIG. 3A is a schematic diagram showing a waveform of the arc cut bias voltage.

FIG. 3B is a schematic diagram showing another waveform of the arc cut bias voltage. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be specifically described with reference to the drawings.

FIG. 1A shows a mold surface in which a Ti metal film is used as a metal layer and a TiN film is used as a ceramic layer on the surface of a molded copper plate base material according to the present invention, and six sets of these are alternately coated (a total of 12 layers). The cross-sectional schematic diagram of a processing material is shown. On the other hand, Fig. 1B shows a schematic cross-sectional view of a current mold surface treatment material in which the surface of a mold copper plate base material is coated with Ni and then plated with Cr to form a two-layer coating.

As is apparent from FIG. 1A, the outline of the mold surface treatment material (molded copper plate) of the present invention is as follows.

1) In order to strongly adhere to the mold copper plate substrate, the metal group Ti, Cr, Ni, B, Si and

A metal layer made of one or more metals selected from Al, and one or more of a nitride, carbide or carbonitride ceramic film of one or more metals selected from the metal group or Two or more types have been adopted as layers constituting the wear-resistant coating. 2) The above metal layer is coated as the innermost layer of the abrasion resistant coating on the surface of the molded copper plate base material to ensure strong adhesion. That is, there was no peeling occurring between the surface of the base material and the metal coating layer composed of one or more metals selected from the metal group.

3) The outermost layer of the coating film on the molded copper plate base material is made of a high hardness ceramic film (a metal nitride, carbide or carbonitride composed of one or more metals selected from the above metal group). (Ceramic film) to improve high strength, abrasion resistance, heat resistance, and ensure heat removal.

4) In order to alleviate the internal strain of the wear-resistant coating on the molded copper plate base material, a metal layer composed of one or more metals selected from the above-mentioned metal group and one or two metal layers selected from the above-mentioned metal group A set of a ceramic layer made of a metal nitride, carbide, or carbon nitride made of at least one kind of metal is coated and coated to form a peel-off of the wear-resistant coating. That cracks were generated in

Here, by using the bias voltage of the arc power as the bias voltage at least at the time of forming the metal layer which is the innermost layer, the adhesion of the above 2) is further improved. The above-mentioned Ti, Cr, Ni, B, Si, and Al are particularly excellent in adhesion to copper or copper alloy among various metals. It was decided to use it as an intermediate layer interposed between ceramic films.

On the other hand, ceramic films made of nitrides, carbides, or carbonitrides of these metals are used as the outermost layer that requires abrasion resistance and heat resistance if they have high strength because of their excellent hardness. I decided that.

Then, between the innermost layer of the metal and the outermost layer of the ceramic, at least one set of the above-described ceramic layer and the metal layer is coated to form a set. Adhesion between the coatings can be further improved, and at the same time, occurrence of cracks in the wear-resistant coating can be prevented. The reason why the above effects can be obtained has not been elucidated yet, but the inventors consider as follows.

That is, the ceramic film is usually hard and has a smaller coefficient of thermal expansion than the metal coating film. Therefore, when a thick ceramic film is coated to ensure high strength, abrasion resistance, and heat resistance, the most strain is accumulated at the interface with the base material, and the film is easily peeled. For this reason, it is difficult to secure adhesion.

On the other hand, when multiple layers of metal layers and ceramic layers are alternately stacked, the strain is effectively released between each metal layer and the ceramic layer (the strain of the ceramic layer is transferred to the metal layer). As a result, it is considered that the adhesion is remarkably improved. Ideally, it is considered that the lamination of the metal shoulder-to-ceramic layers alternately on an atomic basis is optimal for releasing strain.

Surprisingly, it has been confirmed that even when the ceramic layer of the present invention is used for the coating layer, the heat removal properties are not generally deteriorated and the power is significantly improved in some cases. This is because when the ceramic having the composition selected in the present invention is used for the outermost layer, the wettability between the ceramics and the molten mold flux as a lubricant is remarkably improved, and as a result, the thermal conductivity of the coating film by the ceramic layer is increased. It is considered that a sufficient heat removal performance can be obtained by compensating for the decrease.

In order to obtain the above-mentioned heat removal effect, it is preferable that the surface roughness of the ceramic of the outermost layer be in the range of 5 / zm or less in arithmetic average roughness Ra. The use of Ti-based carbides and nitrides, especially TiN, in the ceramic layer has a remarkable effect, and the heat removal is 10 to 40% more than that of a general molded copper plate with a metal plating on a copper plate. High. In the present invention, the thickness of each metal layer including the innermost layer is about 0.1 to 5.0 / zm, and the thickness of each ceramic layer including the outermost layer is about 0.1 to 5.0111. It is preferable that the total thickness, that is, the thickness of the abrasion-resistant coating is about 1.0 to 50 μηι.

Further, in the present invention, it is necessary to coat at least two sets of the metal layer and the ceramic layer (including the innermost layer and the outermost layer) on the surface of the base material. Preferably, the above sets are three or more sets, more preferably five or more sets.

The film thickness of each layer is determined by the number of layers and the total thickness, etc., depending on the above-mentioned effects of improving the adhesiveness, the abrasion resistance required for the film, and the cost of multilayering and thickening the film. Good.

In order to further improve high-strength abrasion resistance and heat resistance without deteriorating adhesion, the coating thickness of metal and ceramic layers should be changed in the film thickness direction. It is preferred that Specifically, it is preferable that the coating thickness of each layer is gradually increased from the innermost layer to the outermost layer, and it is particularly preferable that the ceramic layer is coated such that the coefficient of thermal expansion gradually decreases. The number of thermal expansions of the ceramic layer can be controlled by the composition, surface condition, and the like.

—For example, the coefficient of linear expansion depends on the type of material.

For ΉΝ 9.4 x l0- ⁶ / ° C

Ti 8.6 χ 10- ⁶ / ° C

Cu 16.5 x l0- ⁶

It is. Therefore, in the case of these composite substances, the coefficient of linear expansion changes in accordance with the composition ratio as compared with the case of the pure substance. Therefore, if the relationship between the composition ratio and the linear expansion number is measured in advance, the expansion number can be controlled by controlling the composition ratio of the layer. Of course, the method is not limited to the above. In addition, it is desirable to coat the surface to be coated before the coating from the viewpoint of improving the adhesion. The outline of a manufacturing method for suitably obtaining such a mold surface treatment material for continuous manufacturing is as follows.

5) In order to strongly adhere the mold copper plate base material and the metal layer, or the metal layer and the ceramic layer, avoid the change of the base material due to the heat effect at high temperature due to the surface coating treatment. Therefore, a PVD that can be coated at a relatively low temperature (below 300) has been adopted.

6) Particularly preferably, an HCD or an arc discharge method, which has an excellent ionization rate among PVD, is employed to firmly connect the molded copper plate base material and the metal layer and the metal layer and the ceramic layer. Bonding and force avoids substrate changes due to thermal effects at high temperatures.

7) Particularly preferably, at least at the time of coating the innermost metal layer, the adhesion of the coating layer to the substrate is further improved by using an arc cut bias voltage as a bias voltage.

8) Preferably, when coating the innermost metal layer, a mixed layer is provided at the boundary between the mold copper plate base material and the metal layer by applying a high bias.

Basically, the PVD method is used for the coating treatment of the present kishin. The PVD method includes a dry printing method such as HCD, arc discharge, and EB (Electron Beam) + RF (Radio Frequency). Particularly, the HCD method, which has an excellent ionization rate and enables high-speed film formation, is used. It is preferable to employ an arc discharge method. At this time, these two methods may be used in combination. When coating the outermost layer, use a smooth and delicate ceramic core. The one-touchable HCD method is particularly advantageously adapted. Here, the present inventors conducted research on the composite coating of the present invention with the aim of further improving durability, and as a result, when coating a metal layer or a ceramic layer, the bias voltage of the arc power was used as the bias voltage. I learned that it is extremely effective in achieving the intended purpose. Here, the bias voltage is applied such that the copper plate is negative with respect to the ground.However, thereafter, the absolute value of the potential difference between the ground and the copper plate is used as the bias voltage value, and high bias means that this bias voltage value is large. Shall be referred to.

In other words, when the arc voltage is used as the bias voltage for coating the metal layer or the ceramic layer, the ionized particles are stably deposited on the substrate by preventing abnormal discharge caused by foreign matter. As a result, the occurrence of cracks and peeling of the coating film was significantly reduced, and an advantageous improvement in durability was achieved.

Here, the bias voltage of the arc cutter will be described. The arc cut bias voltage waveform is assumed to be two cases as shown in Fig. 3A and Fig. 3B. In each case, the voltage rises sharply (linearly) when the voltage rises. Rather, the abnormal discharge can be effectively prevented by starting up somewhat gently (parabolic or stepwise).

Note that the type of arc cut shown in FIG. 3A is also called an arc cut or an arc check, and usually a D Cm¾I having a thyristor function is used. On the other hand, the type shown in FIG. 3B is also called a pulse. The type shown in Fig. 3A is more commonly used for arc cutting, but the type shown in Fig. 3B is also used in some cases with slightly different effects. As described above, when the arc voltage of the arc cut is used, the ionized particles can be stably supplied, so that the adhesion is significantly increased, and peeling of the wear-resistant coating is advantageously avoided.

Therefore, from the viewpoint of preventing the entire covering shoulder (abrasion-resistant coating) from peeling, it is strongly recommended to use an arc-cut bias voltage at least when forming the innermost metal layer.

Needless to say, if a bias voltage of an arc cut is used in forming all the layers, the adhesion between the coating layers is improved to flj, and the best result is obtained. Then, in the above-mentioned coating, by using an arc-cut bias voltage as a bias voltage, ionized metal particles are driven deep into the lower layer, and a mixed layer of these metals is formed densely at the boundary between the lower and upper layers. As a result, the two are more firmly joined, and a further improvement in adhesion is achieved.

Here, a preferable range of the voltage applied by the above-described arc cut bias voltage is 10 to 1000 V. In order to secure strong adhesion to the substrate, it is desirable to use a high-bias discharge coating method in which coating is performed under a high bias voltage application, especially for the innermost metal coating. Here, a particularly preferable applied voltage in such a high bias discharge coating method is 50 to 1000 V.

When such a high bias discharge coating method is used, ionized metal particles are driven deep into the substrate when the innermost metal layer is coated, and a mixed layer of these metals is formed at the boundary between the copper plate substrate and the innermost metal layer. As a result, there is an advantage that the two are more firmly joined, and the adhesion is further improved. In the mixed layer formed by such a method, the ratio of the innermost layer metal in the layer is preferably about 10 to 50 mass%. In the present invention, abrasion resistance and heat resistance can be obtained with high strength by the above surface coating (abrasion resistant coating). There are no special restrictions. That is, in recent years, a precipitation hardening type copper alloy has been used as a molded copper plate base material in order to increase the material strength at a high temperature, but it is not necessary to secure the base material strength particularly in the present invention. . Therefore, for example, various commercially available copper sheets and copper alloy sheets for continuous production can be used without any problem.

The thickness of the copper plate is designed according to the application and the size of the piece, but in the case of slab structure, it is generally 30 to 60 mm.

The surface of the copper plate is made of various metals or ceramics in advance as an underlayer for the above-mentioned abrasion-resistant coating (alternate multilayer coating layer composed of a metal layer and a ceramic layer including the innermost layer and the outermost layer). The undercoat may be provided with one or more layers. In particular, coatings containing one or two selected from Ni, Cr, Fe, Co, Mo, ff, Al, and Y (ie, 50 mass% or more of the base coat) (so-called metal plating layers) Since the copper plate and the abrasion-resistant coating layer have good adhesion, they are suitable as the undercoat. Among them, it is preferable to use one or two selected from Ni, Cr, Fe and Co as main components.

These coatings are applied to a conventional molded copper plate by a method such as wet plating or thermal spraying, and generally have a thickness of about 30 to 2000 μαα. In the present invention, the effect of these metal-plated layers is not necessarily required, but since these metal elements have good adhesion to the copper plate, the abrasion resistance of the present invention « luck There is no problem if it is formed on a layer.

Therefore, when the abrasion-resistant coating of the present invention is applied to an existing molded copper plate, it is not necessary to take extra labor and cost to separate the metal plating layer.

The molded copper plate of the present invention may be applied to the entire inner side of the mold, or may be applied only to important parts. For example, if the heat removal function is emphasized, the material of the present invention having a high heat removal function (for example, Ti-based, In particular, the use of a TiN coating layer) can be considered. On the other hand, if durability is important, it is conceivable to apply the high hardness (for example, Si type) material of the present invention only to the lower part of the mold (the lower half, around 30 mm from the end). Can be Of course, for example, if a mold is formed by applying the present invention copper plate adopting the TiN coating layer in the upper half and the present invention copper plate adopting the SiC coating layer in the lower half, it is a preferable combination taking advantage of the respective advantages.

(Example)

Example 1

On the surface of a base material (Cr: 1. Oraass%, Zr: 0.1 mass%, balance: Cu) consisting of a molded copper plate, using an arc discharge method, initial bias: under the application of an arc cut bias voltage of 400 V,

An innermost layer of Ti metal (thickness: 3.0 / zm) was formed. Then, in the same way, TiN (thickness: 3.0 / zm)

→ Ti (thickness: 3.0 μια) → TiN (thickness: 3.0) → Ti (thickness: 3.0) → TiN (thickness: 3.0) was laminated to form a composite film having a thickness of about 18 m. Then, using the HCD method, a Ti (thickness: 2.0 / zm) → TiN (thickness: 2.0 / zm) film was formed under the application of an initial bias of 400 V (normal bias voltage, the same applies hereinafter). An eight-layer, molded copper plate (Invention Example 1) having a wear-resistant coating with a total thickness of about 22 m was produced. The innermost layer of Ti metal (thickness: 3.0 m) was formed on the surface of the same base material using an arc discharge method with an initial bias of 250 V applied. Then, in the same manner, TiN (thickness: 3.0 ra) → Ti (thickness: 3.0 μηι) → TiN (thickness: 3.0) → Ti (thickness: 3.0 / xm) → TiN (thickness: 3.0) is laminated, and the thickness is approximately 18 a m-thick composite film was formed. Thereafter, using the HCD method, a film of Ti (thickness: 2.0 urn) → TiN (thickness: 2.0 ^ ra) is formed under an initial bias of 400 V, and a total of eight layers and a total thickness of about 22 A molded copper plate (Invention Example 2) having a wear-resistant coating of / zm was prepared.

The results of examining the hardness (surface hardness; test load: 400 g) and adhesion of the surface-coated molded copper plate thus obtained are shown in FIGS. 2A and 2B. Here, the adhesion was measured by applying a Rockwell C diamond tip (tip radius 0.2 mm, tip angle 120 ° hardness Hv8000 or more) to the surface of the surface-coated mold copper plate using a pulling method, and continuously applying the tool. The substrate was pulled while applying a gradually increasing load, and the critical load was evaluated when a streak-like fracture (film peeling) occurred at the end of the flaw. As a comparative example, Ni plating (thickness: 0.5 band) was applied to the surface of the same base material as the invention example by a wet plating method according to the conventional method, and then Cr plating (thickness: 30 mm) was further applied. / zm). The results of a similar investigation performed on the obtained surface-coated molded copper plate are also shown in FIGS. 2A and 2B.

As is clear from FIGS. 2A and 2B, it is understood that Inventive Example 1 and Inventive Example 2 are significantly superior in both hardness and adhesion in comparison with Comparative Examples. In addition, it can be seen that Example 1 using the arc-cut bias voltage is superior in adhesion to Invention Example 2. In addition, when stainless steel slabs were continuously manufactured using the above-described surface-coated molded copper plates, cracks were not generated even after the invention example 1 and the invention example 2 after 1000 charge fabrication. Yes, it was confirmed that good durability could be obtained in actual operation. In contrast, in the case of the current surface-coated molded copper sheet represented by the comparative example (comparative example), cracks occurred in the surface coating layer after 300 to 600 charge production. Example 2

Substrate made of molded copper plate (No. 3-14; Cr: 1.5 mass%, Zr: 0.15 mass%, balance: Cu), base material made of copper plate with Ni plating on the surface (No. 15, 16) and the surface of a base material (No. 17, 18) consisting of a copper plate with Ni--Cr sprayed on the surface, as shown in Table 1, by using various PVD methods, Ceramic layers were alternately laminated to produce a surface-coated molded copper plate.

Table 1 also shows the results of an examination of the hardness and adhesion of the obtained surface-coated molded copper plate in the same manner as in Example 1.

In addition, in the column of “whether or not to use the arc cut bias voltage” in Table 1, those with “Yes” applied the arc cut bias voltage to all layers. In the case of “None”, a bias voltage that does not cause arc cutting (voltage intensity is the same as “Yes”) was applied to all layers.

Abrasion resistant coating: ^ TJW ヽ

種類 Kind of metal layer, ceramic layer, number w ± force (thickness: m) Shelf ^ ftJPa)

See nothing (grant

Ti— TiN- Ti-TiN- Ti-TiC- Ti-TiC 8 ID) method

A (2 ς〗 (2 5) (9 ς) (2 5) (9 (9 0 5) (9 5) (20) or 1 1 ク

5 Cr-CrN- Cr—CrN— Cr-CrN 6 H3) Method Yes (150) 1900 161 c

0 (3.0) (3.0) (2.0) (2.0) (2.5) (2.5) (15)

ICxAJ

7 Ni- NiN- Ni- NiN- Ni- TiC— Ni— TiC-M—TiC 10 ED method Yes (100) 1700 160

8 (a $) (a 5) (a 9 (a ø (a o) (a o) (2.5) (2.ø e.5) (2.5) (30) None 1600 119

9 Β — ΒΝ — Β — ΒΝ — Β — ΒΝ 6 Yes 2500 163

10 (3.0) (3.0) (3.0) (3.0) (3.0) (3.0) (18) No law 2400 139

11 Si— Si x-Si- Siik-Si-SiC- Si-SiC- Si-SiC 10 SiNx: The Yes (80) 2700 150

(2.o) o) (2.o) o) o) (a o) (a o) o) G.5) (2.5) (25) Net

12 Data method None 2600 118

SiC

w

13 Al—fine Al— A1N— Al— A1C— Al—A1C 8 Yes (100) 2400 159 (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) (2 .5) (2.5) (2.5) (20)

14 pieces

Tojita

Law

15 Ti- TiN- Ti-TiN- Ti-TiC-Ti-TiC 8 KB method Yes (150) 2500 170

16 (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) <¾)) None 2300 115

17 Ti- TiN- Ti-TiN- Ti— TiC-Ti-TiC 8 KD method Yes (100) 2500 150

18 (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) (2.5) None 2300 120 As shown in the table All the surface-coated molded copper sheets obtained according to the present invention were able to obtain not only high hardness but also excellent adhesion. Also, it can be seen that when the arc cut bias voltage is used, the adhesion and the like are further excellent.

Example 3 As an example of the invention, a molded copper plate having a Ti-TiN-based surface coating shown in Example 1 (deposited) 16 types of surface-coated molded copper plates (Inventive Examples 3 to 18) shown in Examples 1 and 2) and Example 2 were prepared.

In addition, as comparative examples, a mold copper plate having a (Ni + Cr) plating shown in Example 1 (Comparative Example 1) and a mold copper plate in which TiN was laminated on a copper plate base material by 10 / zm by an arc method (Comparative Example) Example 2), Molded copper plate with 10 / Zm layered nitride on the copper plate substrate by HCD method (Comparative Example 3), Ni-P plating by arc method as base layer on copper plate substrate (thickness) Molded copper plate (Comparative Example 4) with titanium nitride (thickness: 7 / zm) laminated thereon by HCD method, and Cr plating by wet plating as a base layer on the copper plate substrate (thickness: 30; m) and a chromium nitride (thickness: 5 μm) laminated thereon by the HCD method (Comparative Example 5), and Ni—Cr sprayed (thickness: 1 A thigh) and a molded copper plate (Comparative Example 6) plated with Cr (thickness: 30 / im) were prepared.

Using these surface-coated molded copper plates on the short side of the 錄 type, continuous mirror making was performed by a continuous machine.

The manufactured steel types are stainless steel (SUS 430 steel, SUS 304 steel) and high carbon steel (SK5 to SK2) specified in JIS Handpuck Steel. The continuous machine is a vertical bending machine, and the size of the machine is 200 slabs in thickness, 750 to 1240 mm in width, and 915rara in length. The production speed is 0.9 to 1.3 m / min for stainless steel and 0.8 to 1.2 m / min for high carbon steel.Evaluation of heat release is 1.0 m / min, slab width 1000 to The test was performed at 1100 mm. The properties of the mold flux used were: solidification temperature 1100 ° C, viscosity at 1300 2.0 poise, basicity

(Ca0 / Si02) 1.05.

For each mold, 1 heat: 150 tons of molten steel were manufactured in a total of 500 units. After producing 500 heats in this way, the condition of the surface coating on the mold copper plate (crack, peeling, Was observed. 'The results obtained are shown in Table 2.

Table 2 Awake short side copper plate

Existence of cracks Exfoliation Existence of wear Invention example 1 None None None

II 2 None None None

II 3 None None None

"4 None None None

II 5 None None None

"6 None None None

"7 None None None

"8 None None None

"-9 None None · None

II 10 None None None

"11 None None None

, '12 None None None

"13 None None None

"14 None None None

"15 None None None

"16 None None None

"17 None None None

"There are no 18 's

Comparative Example 1 None None

2 Number of names over the entire surface Many over the entire surface

3 Many over the entire surface Many over the entire surface

,, 4 Around the bottom of the meniscus, peeling at the lower end and cracking of the number of copper plates at the peeled portion at the lower end.

(5) Many peels at the lower end near the meniscus.

Gas 6 None None Copper plate at the peeled part at the bottom As is evident from Table 2, in all of the invention examples, no cracking, peeling or abrasion occurred in the surface coating layer. On the other hand, in Comparative Examples 1 and 6, glazed abrasion was observed at the lower end of the »S short side. Further, in Comparative Examples 2 and 3, many cracks and peeling occurred on the entire surface, and in Comparative Examples 4 and 5, many cracks were observed near the meniscus and peeling was observed at the lower end.

Example 4 With respect to each of the examples and comparative examples adopted in Example 3, the heat removal was evaluated. The heat removal was calculated from the temperature difference between the inlet and outlet sides of the cooling water for the copper plate and the flow rate of the cooling water, and was expressed as the ratio to Comparative Example 1. In order to evaluate the uniformity of cooling, the temperature was measured at intervals of 1 second at 10 Omm below the meniscus in the center of the short side width and at a depth of 10 mm from the surface, and the standard deviation in 10 minutes was obtained. Table 3 shows the results.

Table 3 Surface roughness Heat removal ratio Copper plate temperature

Ra (χ &) standard deviation CC)

Invention Example 1 1.34 1.11-1.35 1.9

// 2 0.12 1.15-1.45 2.1

"3 0.34 1.01 to 1.09 2.5

"7 3.19 1.05 ~: 1.11 2.7

a 9 0.12 0.94-1.05 3.5

"11 1.26 0.97 to 1.07 4.1

Comparative Example 1 0.11 1.0 5.5

"2 5.3 1.05-1.20 3.3

"4 6.5 1.03 to 1.15 2.8

a 6 0.33 0.95 to 1.05 4.6 As is evident from Table 3, all of the inventive examples exhibit at least good heat removal properties comparable to those of the current copper sheet material (Comparative Example 1). There is little difference in heat removal depending on the position of the plate surface. In particular, the heat removal was improved in the Ti system (Invention Examples 1, 2, 3, and 7) compared with the current material, and in particular, the TiN system (Invention Examples 1 and 2) improved by more than 2015%. In addition, these copper sheet materials had a small standard deviation of the copper sheet temperature and were excellent in the uniformity of heat removal. In general, there is concern about the occurrence of minute vertical cracks on the surface of the piece due to an increase in the amount of heat removed, but such cracks were not generated in the piece manufactured using the key of the present invention. Therefore, by using these molded copper sheet materials, it is possible to cool the filler material uniformly and uniformly, and it is expected that the production speed of the slap can be increased.

On the other hand, in Comparative Examples 2 and 4 using TiN for the outermost layer, the roughness was out of the preferred range, and the effect of improving heat removal was small. In each of the above embodiments, the case where the molded copper sheet of the present invention is applied to the short side of the mold is mainly described. However, the same effect can be obtained when applied to the long side of the mold. Has been confirmed. Industrial applicability

Thus, according to the surface-coated molded copper sheet of the present invention, the hardness of the solidified shell during hot working is excellent even if it is actually subjected to continuous working of stainless steel or high carbon steel. In addition, it is possible to efficiently produce high-quality pieces while maintaining the heat removal property, especially at the time of high-speed production, which is extremely industrially effective.

Claims

The scope of the claims

1. A mold copper plate suitable for continuous production of molten metal,

A base material substantially made of a copper or copper alloy plate material,

Having a coating layer provided on the surface of the base material,

The coating layer,

An innermost layer made of one or more metals selected from the group of metals Ti, Cr, Ni, B, Si and Al;

A layer formed on the innermost layer and formed of a nitride, carbide or carbonitride of one or more metals selected from the metal group; and one or more layers selected from the metal group An intermediate layer in which one or more sets of metal layers are alternately stacked;

An outermost layer formed of a nitride, carbide, or carbonitride of one or more metals selected from the metal group formed on the intermediate layer

A molded copper plate for continuous production, characterized by that:

2. The continuous structure according to claim 1, wherein a mixed layer of a metal forming the innermost layer and a metal forming the base material is formed at a boundary between the innermost layer and the base material. Molded copper plate.

3. The request according to claim 1, wherein the base material is obtained by coating the surface of the plate material in advance with one or more selected from M, Cr, Fe and Co. The mold punishment plate for continuous construction as described in 1 or 2.

4. One or more metals selected from the group consisting of Ti, Cr, Ni, B, Si and Al as the innermost layer by the PVD method on the surface of the copper or copper alloy plate material as the base material. A layer composed of a nitride, carbide or carbonitride of one or more metals selected from the metal group, and one or more layers selected from the metal group Money One or more layers consisting of a group of metals are alternately laminated, and a layer made of nitride, carbide or carbonitride of one or more metals selected from the above metal group is formed as the outermost layer. A method for producing a molded copper plate for continuous production, characterized by the following.

5. The method according to claim 4, wherein the innermost layer is formed by a high bias discharge coating method.

6. The method for producing a mold copper sheet for continuous production according to claim 4 or 5, wherein an arc-cut bias voltage is used in forming at least the metal layer as the innermost layer.

7. The base material made of copper or copper alloy, the surface of which is coated in advance with one or more selected from Ni, Cr, Fe and Co. The method for producing a mold for continuous production according to any one of claims 4 to 6, wherein: