WO2005028143A1

WO2005028143A1 - Continuous casting mold and method of continuous casting for copper alloy

Info

Publication number: WO2005028143A1
Application number: PCT/JP2004/013756
Authority: WO
Inventors: Yasuhiro Maehara; Mitsuharu Yonemura; Keiji Nakajima; Naotsugu Yoshida; Masahiro Aoki
Original assignee: Sumitomo Metal Industries, Ltd.
Priority date: 2003-09-24
Filing date: 2004-09-21
Publication date: 2005-03-31
Also published as: JPWO2005028143A1; TW200528213A; EP1688198A4; TWI272145B; JP4333881B2; EP1688198A1; US20060180293A1

Abstract

A continuous casting mold for Cu alloy characterized in that a glassy carbon material, a metallic self-lubricating composite material or a graphite material of over 1.92 bulk density is used at at least a mold portion facing a position of solidification initiation of a Cu alloy melt; or a continuous casting mold for Cu alloy characterized in that at least a mold inside wall facing a position of solidification initiation of a Cu alloy melt is coated with a self-lubricating material or a metallic self-lubricating composite material. There is further provided a method of continuous casting for copper alloy characterized in that in the continuous casting of Cu alloy conducted with the use of the above mold in accordance with the slab intermittent drawing-out technique, a vibration with a frequency being larger by at least two digits than that of slab intermittent drawing-out vibration, the vibration having a component perpendicular to the direction of drawing-out, is applied to the mold, or a lubricant or seizure preventive agent is continuously fed into the space between the mold and any solidified shell.

Description

Specification

Continuous production mold and continuous production method of copper alloy

Technical field

The present invention relates to a continuous manufacturing method and a continuous manufacturing method for a Cu alloy. In particular, the present invention relates to a 铸 type used in a direct connection type continuous forming machine in which a holding furnace is directly connected to a 铸 type, and a continuous manufacturing method of a Cu alloy using the 铸 type.

Background art

[0002] In recent years, the IT boom has been used in electrical and electronic components such as lead frames, terminals, connectors, springs, and contact elements in the movement of electrical equipment for mobile phones, personal computers, and automobiles. The performance of Cu alloys is becoming increasingly important. Typical required characteristics are firstly high strength for light weight dangling, and secondly, high conductivity dangling for suppressing an increase in electric resistance due to a decrease in cross-sectional area due to light weight dangling. . On the other hand, there are also important issues such as improvement of workability such as bending work accompanying downsizing of parts, improvement of heat resistance to withstand use even in relatively harsh environments, and improvement of fatigue resistance. Has become.

[0003] Such a high-strength and highly-conductive material is used in an environment such as an ammunition warehouse or a coal mine where excellent spark generation resistance is required in addition to the performance required for conventional tools such as wear resistance. It can also be applied to safety tool materials used below. As such a material, for example, there is an example of a Cu alloy in Patent Document 1.

[0004] The continuous structure of a Cu alloy is roughly classified into the following two methods.

[0005] The first method is a direct connection type continuous structure (a horizontal type, a vertical type, or the like) using a graphite mold directly connected to a holding furnace. In the direct connection type continuous structure, it is extremely difficult to supply a lubricant. Therefore, a graphite material having a self-lubricating property and a high thermal conductivity and a bulk density of 1.7 to 1.9 is generally used as a 铸 -type material. This method achieves a high V ヽ cooling rate in the cooling process after solidification, and has a small thickness that reaches the final product without going through the subsequent solution treatment and hot working! Suitable for getting pieces! /

[0006] In a second method, Cu is supplied through a nozzle immersed in a molten metal pool described in Patent Document 1. It is a non-direct connection type continuous structure (a vertical type, a curved type, a vertical curved type, etc.) that pours into a mold made of a metal material or an alloy material typified by a Cu alloy. In the non-direct connection type continuous production, the nozzle thickness is limited to a relatively large one of about 100 mm or more because the nozzle is immersed in the molten metal pool in the mold. Since this method has a low cooling rate in the cooling process after solidification, a hot process such as solution treatment or hot working is indispensable until a final product is obtained.

[0007] From these two types of continuous manufacturing methods, an appropriate method is selected according to the required alloy composition, the piece cross-sectional shape, the cooling rate, and the like. In general, when a high cooling rate is required or when the Cu alloy does not contain an element having high reactivity with C in the graphite material, the former (direct connection type) is adopted, and a large cross section size piece is used. The latter (non-coupling type) is often used when Cu alloy is required or when the Cu alloy contains an element that is highly reactive with C in the Dalaphite material.

Patent Document 1: JP-A-61-250134

Disclosure of the invention

Problems to be solved by the invention

[0009] A first object of the present invention is to provide a continuous forming mold suitable for a direct-coupled continuous forming of a Cu alloy containing an alloy element that easily reacts with C such as Zr, Ti, and Cr. A second object of the present invention is to provide a continuous method for producing a Cu alloy using the mold. It should be noted that the continuous structure in the present invention has a great effect also on the continuous structure of a material other than the Cu alloy, particularly a non-ferrous metal material.

Means for solving the problem

[0010] New aiming for higher strength and higher conductivity! / ヽ Cu alloys contain elements that react easily with C, such as Zr, Ti, and Cr. In addition, a high cooling rate is required in the cooling process after solidification to achieve good properties. However, it was found that these alloys had the following problems caused by the reaction between C in the graphite material, which is a 铸 -type material, and the above elements.

[0011] That is, when the above-mentioned Cu alloy is applied to a direct-connection type continuous structure, an element that easily reacts with C such as Zr, Ti, and Cr in the molten metal and C in the graphite material react with each other, resulting in initial formation. And The solidified shell is seized to the shape 铸, and the pull-out resistance is significantly increased. As a result, problems such as 铸 mold wear due to mold stamping and 铸 inability to pull out the piece are caused. As described above, it was difficult to apply the direct connection type continuous structure, and this also restricted the development of the alloy itself.

[0012] The present invention has been made to solve these problems and suppresses seizure of an initially formed solidified shell to a mold, and is sufficiently high in a cooling process after solidification! The present invention relates to a continuous production mold capable of obtaining a cooling rate and a continuous production method using the same, and the invention of the following continuous production mold (1)-(5) and the continuous production method (6) — The invention of (14). Hereinafter, these are referred to as the present invention (1) and the present invention (14), respectively. These inventions may be collectively referred to as the present invention.

[0013] (1) A glassy carbon material, a metal-based self-lubricating composite material, or a graphite material having a bulk density of more than 1.92 is used for at least the 铸 -shaped portion facing the solidification start position of the molten Cu alloy. The continuous production type for Cu alloy.

[0014] (2) At least one of a graphite member, a single member selected from a graphite material member, a ceramic material member, and a metal material member, or a combination of two or more members. A continuous production mold for Cu alloys, characterized in that the internal wall of the copper mold facing the solidification start position of the molten Cu alloy is coated with a self-lubricating material or a metal-based self-lubricating composite material.

(3) A combination of two or more members selected from a self-lubricating material member, a metal-based self-lubricating composite material member, a graphite material member, a ceramic material member, and a metal material member A self-lubricating material member or a metal-based self-lubricating composite material member is used as an inner wall member of at least a shape corresponding to at least the solidification start position of the molten Cu alloy. , Continuous fabrication type for Cu alloy.

(4) A combination of two or more members selected from a self-lubricating material member, a metal-based self-lubricating composite material member, a graphite material member, a ceramic material member, and a metal material member铸, characterized in that at least the 铸 inner wall facing the solidification start position of the molten Cu alloy is covered with a self-lubricating material or a metal-based self-lubricating composite material. , Continuous fabrication type for Cu alloy.

(5) It is confirmed that the 铸 -shaped inner wall facing the molten Cu alloy is covered with a ceramic material. The continuous structure for a Cu alloy according to any one of (1) to (4) above, which is characterized in that:

[0018] (6) A method for continuously producing a Cu alloy, wherein the method is one of the above (1) and (5), and is continuously produced by an intermittent drawing method of a piece.

(7) When continuously producing a Cu alloy by the intermittent drawing method of a piece, the number of cycles must be at least two orders of magnitude greater than the number of intermittent drawing cycles of the piece, and it is perpendicular to the drawing direction. A continuous manufacturing method for a Cu alloy, comprising applying vibration having a component to a mold.

(8) When continuously producing the Cu alloy by the intermittent drawing method of the piece, a lubricant or an anti-seizure agent is continuously supplied between the inner wall of the mold and the piece. Continuous manufacturing method of alloy.

(9) When continuously producing a Cu alloy by the intermittent drawing method of a piece, the cycle number is at least two orders of magnitude greater than the number of intermittent drawing cycles of the piece, and is perpendicular to the drawing direction. A continuous production method of Cu alloy, comprising: applying vibration having a component to a mold; and continuously supplying a lubricant or an anti-seizure agent between an inner wall of the mold and the piece.

[0019] (10) When the Cu alloy is continuously manufactured by the intermittent drawing method of the piece, the number of cycles is at least two orders of magnitude larger than the number of intermittent drawing cycles of the piece and is perpendicular to the drawing direction. (6) The method for continuous production of a Cu alloy according to the above (6), wherein vibration having various components is applied to the mold.

(11) When continuously producing a Cu alloy by the intermittent drawing method of the piece, a lubricant or an anti-seizure agent is continuously supplied between the inner wall of the mold and the piece. The continuous production method of the Cu alloy according to the above (6) or (10).

[0021] (12) Cu alloy, the mass ^{_{0/0, Cr: 0.01- 5}} %, Ti: 0.01- 5%, Zr: 0.01- 5%, Nb: 0.01 one 5%, Ta: 0.01 one 5% , Al: 0.01-15%, Mo: 0.01-5%, V: 0.01-15%, Co: 0.01-15%, Mn: 0.01-5%, Si: 0.01-5%, Be: 0.01-5% and Hf: A continuous method for producing a Cu alloy according to any one of the above (6) to (11), characterized by containing one or more components selected from among 0.01-5%.

(13) Cu alloy force Further, in mass%, at least one of the following first group forces up to the third group: (12) The continuous production method for a Cu alloy according to the above (12), wherein one or more selected alloy components are contained in a total amount of 0.001 to 5% by mass.

Group 1: One or more selected from among P, B, Sb, Bi, Pb, Cd, S and As 0.001-1% by mass in total

Group 2: One, two or more selected from Sn, Ag, Zn, Ni, Au, Pd, Fe, W, In, and Ge 0.01-5% by mass in total

Group 3: One or two selected from Te, Se, Sr, Tl, Rb, Cs, Ba, Re, Os, Rh, Po, Ga, Tc, Ru, Pd, Ir, Pt and Ta Above total 0.01-3% by mass

[0023] (14) Cu alloy strength Further, one or more alloy components, in which the power is also selected from among Li, Ca, Mg and rare earth elements, are contained in a mass% of 0.001-2% by mass in total. (12) or (13), a method for continuously producing a Cu alloy.

The invention's effect

[0024] According to the present invention, it is possible to provide a continuous structure mold capable of continuously producing sound pieces efficiently and stably. Further, it is possible to provide a method for continuously producing a Cu alloy, which is excellent in properties of a final product after processing and heat treatment, for example, strength, conductivity, or fatigue strength. In particular, a great effect can be obtained when applied to the structure of a Cu alloy containing Zr, Ti, Cr, Ta, V, etc., which are elements that easily form carbides. In addition, the present invention has a great effect on materials other than Cu alloys, especially non-ferrous metal materials.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

FIGS. 1 to 7 show an example of a direct connection type horizontal continuous structure according to the present invention. In each of the figures, the type III is directly connected to the refractory of the holding furnace wall 2 that contains the molten metal 1 of the Cu alloy. In order to protect the connection part of the holding furnace wall, a connection refractory such as a feed nozzle may be provided between the holding furnace wall and the mold.铸 A cooling chamber 1 having a structure for flowing cooling water etc. inside the mold is placed in close contact with the outside of the member 3 constituting the The heat is removed by primary cooling of the molten metal and solidification proceeds to form piece 4. After leaving the mold, the piece 4 can be water jet, air jet or air-water mixed. Secondary cooling 6 is performed by joint injection and the like. The piece 4 is withdrawn in the withdrawal direction 7.

[0027] The mold according to the present invention includes a coating 8 on the inner wall of the mold corresponding to the solidification start position 10 of the Cu alloy melt and a mold of the mold corresponding to the Z or the Cu alloy melt upstream of the solidification start position. Some have an inner wall coating 9.

In addition, the 铸 shape may include a plurality of members. That is, the 铸 shape may be configured by the member 3 forming the 铸 shape and the other member 3 ′ forming the 铸 shape.

[0028] In addition, during preheating before fabrication, the inner wall surface of the mold may be deteriorated by oxidation. In order to prevent this, it is preferable to apply an oxidation resistant coating such as metal plating to at least a portion corresponding to the solidification start position of the inner wall of the mold. The coating material having oxidation resistance is not particularly limited, but is preferably a material which can be easily dissolved in a molten metal at the time of production and does not harm the properties of the final product. For example, in the case of incorporating a Cu alloy, it is preferable to use Cu as a coating material, and its thickness of about several / zm is sufficient.

[0029] Here, the solidification start position in the present invention is defined as follows. The Cu alloy that has flowed into the mold 溶 is a molten metal upstream of the mold 铸, and an initial solidification shell is formed at a certain position in the mold 铸. This solidified shell forming position is referred to as a solidification starting position. The solidification start position slightly varies depending on the manufacturing conditions such as the temperature of the molten metal in the holding furnace, the mold cooling, and the drawing speed. Therefore, the solidification start position refers to the “region where solidification shell formation occurs” with a certain width in the drawing direction.

FIG. 1 to FIG. 7 show examples of direct connection type horizontal continuous structure type molds according to the present invention. In the case of direct connection type vertical continuous structure type molds, FIG. It is like rotating 90 degrees clockwise.

[0031] Hereinafter, the continuous sintering mold of the Cu alloy according to the present invention will be described in detail for each of the types (A) to (E). Further, a method of continuously forming a Cu alloy using these molds will also be described.

(A) A Cu alloy characterized by using a vitreous carbon material, a metal-based self-lubricating composite material or a graphite material in at least a 铸 -shaped portion corresponding to a solidification start position of a molten Cu alloy. Continuous production type. FIG. 1 shows an example of a continuous structure according to the present invention. A member 3 constituting a mold including a mold portion corresponding to a solidification start position 10 of a molten Cu alloy is provided with a glassy carbon material. FIG. 1 is a schematic view of a continuous structure for Cu alloy using a metal-based self-lubricating composite material or a graphite material.

[0034] By using a vitreous carbon material, a metal-based self-lubricating composite material or a graphite material at least for the 铸 -shaped portion opposite to the solidification start position of the molten Cu alloy, a sound piece can be continuously and efficiently improved. It can be manufactured stably. It is preferable to use a graphite material having a bulk density of more than 1.92.

In addition, it is possible to provide a method for continuously manufacturing a Cu alloy, which is excellent in characteristics of a final product after processing and heat treatment, for example, strength, conductivity, or fatigue strength. Particularly when applied to the structure of a Cu alloy containing Zr, Ti, Cr, Ta, V, etc., which are elements that easily form carbides, a great effect can be obtained.

[0035] The present inventors have found that, when a direct connection type continuous structure is performed by a conventional mold using a graphite material having a bulk density of 1.7 to 1.9, a large number of open pores existing on the surface of the graphite material are filled with Cu alloy. It was found that the molten metal penetrated, and the solidified shell that had initially formed was seized on the mold 铸, and as a result, mold 铸 was worn due to mold eruption, and 铸 pieces could not be pulled out. In addition, when an element that easily reacts with C such as Zr, Ti, and Cr is included, carbides are further generated at the interface between the molten metal and the mold, and the initially formed solidified shell is seized into the mold. As a result, it was found that the mold was worn due to mold shaping, and that one piece could not be pulled out.

[0036] In order to solve this problem, (a) a 铸 -type material that does not easily react with the elements in the molten metal, or (b) the number of open pores on the surface is very small分 The use of a shaped material was effective.

That is, as the first means, it is effective to use a glassy carbon material or a metal-based self-lubricating composite material from the viewpoint of the reactivity between the の -shaped material and the molten metal.

It has been found that the glassy carbon material has a property that it is less susceptible to oxidation than the graphite material and is less likely to react with Zr, Ti, Cr and the like, and thus can sufficiently achieve the object.

[0038] Metal-based self-lubricating composite materials are MoS, WS, BN, and mica in a metal material matrix. Such a cermet in which a self-lubricating material that hardly reacts with Cr and Zr is dispersed and mixed, and it has been found that this can sufficiently achieve the object.

The method for producing the composite material is not particularly limited. For example, a method in which a metal material powder and a self-lubricating material powder are mixed, compression-molded, and then sintered may be used! The content of the self-lubricating material in the composite material is not particularly limited, but is preferably 10% by volume or more, more preferably 30% by volume or more, and further preferably 80% by volume or more. When the content of the self-lubricating material is increased, the reaction resistance and lubricity are improved, but the mechanical properties of the composite material, such as strength and thermal shock resistance, are reduced. Therefore, it is preferable to suppress the content to 85% by volume or less.

Further, as the metal material constituting the composite material together with the self-lubricating material, a metal material or an alloy material which is not particularly limited can be used. Since it is a 铸 -shaped material in contact with the molten Cu alloy, it is preferable to use a metal material and / or an alloy material having a high melting point and high thermal conductivity. Specific examples include Cu alloys, stainless steels, Ni alloys, Co alloys, and W alloys.

As a second means, it is effective to use a high bulk density graphite material having almost no open pores. As a result of various studies, it has been found that if the bulk density exceeds 1.92, such an object can be sufficiently achieved.

[0040] When continuously forming a Cu alloy by the intermittent drawing method of the piece using this mold, (1) the intermittent bow of the piece is at least two orders of magnitude larger than the number of punching cycles. Vibration having a cycle number and a component perpendicular to the drawing direction is applied to the mold, and (2) a lubricant or anti-seizing agent is continuously supplied between the inner wall and the piece of the mold. By using either one or both of them, a greater effect can be obtained. If one or both of the above measures (1) and (2) are taken, even if a graphite material having a bulk density of less than 1.92 is used as a material for forming the mold, it is possible to obtain a connection between the piece and the mold. Since seizure can be prevented, continuous production is possible.

In addition, after taking one or both of the above measures (1) and (2), if a graphite material having a bulk density of more than 1.92 is used as the material constituting the mold, the piece and the mold will be removed. Since the anti-seizure property is further improved, continuous fabrication can be easily performed. [0041] The intermittent drawing method of the piece reduces the frictional resistance between the inner wall of the mold and the piece and improves the lubricity to produce a sufficiently healthy piece continuously and efficiently. Can

[0042] If a vibration having a cycle number at least two orders of magnitude larger than the number of intermittent drawing cycles and a component perpendicular to the drawing direction is applied to the 铸 type, the same effect can be obtained for a longer time. Can be The frequency is preferably 5000 cpm (83 Hz) or more, more preferably 60,000 cpm (lkHz) or more, which approaches the ultrasonic range.

[0043] The lubricant to be supplied between the inner wall of the 铸 type and the 铸 piece includes MoS, WS, BN, mica,

twenty two

Ultra-fine powder of CaCO, which is hard to aggregate, is recommended

Three

The For continuous feeding, a large number of the above fine powders are lubricated with mineral oil, synthetic ester, or a mixture of them, or an anti-seizure agent is provided on the inner wall of the 铸 type using a pressure pump. It is injected through a through hole of about 20 μm. A sufficient effect can be obtained with an injection amount of about 0.1 cc / cm ² 'min, which is about sweating. Such injection was difficult in the prior art, but was made possible by the advancement of nanotechnology, which made it easier to obtain ultrafine powders with diameters on the order of nanometers.

[0044] (B) At least one type selected from a graphite material member, a ceramic material member, and a metal material member or a combination of two or more members, and A continuous production mold for Cu alloys, characterized in that the internal wall of the copper mold facing the solidification start position of the molten Cu alloy is coated with a self-lubricating material or a metal-based self-lubricating composite material.

FIG. 2 is an example of a continuous structural mold according to the present invention, in which the member 3 constituting the mold is formed by one selected from a graphite material member, a ceramic material member, and a metal material member. In a schematic view of a continuous 铸 Cu 铸铸 Cu され Cu Cu Cu Cu 自己自己自己自己自己、、、、、、、、構成されされされされされされis there.

The 本体 -shaped main body is constituted by one selected from a graphite material member, a ceramic material member, and a metal material member, and the 内 -shaped inner wall is coated with a self-lubricating material or a metal-based self-lubricating composite material. By using a metal mold with a sound, continuous healthy pieces It can be efficiently and stably manufactured. Further, it is possible to provide a method for continuously manufacturing a Cu alloy, which is excellent in characteristics of a final product after processing and heat treatment, for example, strength, conductivity, or fatigue resistance. In particular, a great effect is obtained when applied to the structure of a Cu alloy containing Zr, Ti, Cr, Ta, V, etc., which are elements that easily form carbides.

When a graphite material is selected as the mold material, in order to increase the adhesion between the mold material and the coating film, a dense coating material composed of C, for example, a self-lubricating material such as glass is used. It is preferable to select a carbonaceous carbon material, a layered carbon material, or a diamond-like carbon material. Since the surface unevenness of the coating film substantially reflects the surface unevenness of the graphite material itself, it is desirable to select a graphite material having a bulk density as high as possible. Although not particularly limited, the bulk density is preferably 1.7 or more, more preferably 1.8 or more, and more preferably more than 1.92.

[0048] As the ceramic material, an inorganic material composed of one or more selected from oxides, nitrides, carbides, and borides is used. Although not particularly limited, from the viewpoints of mechanical strength and thermal conductivity to be provided as a 铸 -type material, BN materials, sialon materials (Si N -A1N-A1 O-SiO phase diagram)

3 4 2 3 2

Good.

When using a material having low thermal conductivity, it is preferable to take measures such as reducing the thickness of the mold, ie, decreasing the distance between the piece and the cooling chamber. When selecting a ceramic material obtained by sintering BN and Sialon, use a dense coating material composed of a nitride material, such as a self-lubricating material, in order to improve the adhesion between the mold material and the coating film. It is better to select a certain BN material.

[0050] As the metal material, a metal material or an alloy material that is not particularly limited can be used. Since it is a 铸 -shaped material in contact with the molten Cu alloy, it is preferable to use a metal material or an alloy material having a high melting point and high thermal conductivity. Specifically, Cu alloy, stainless steel, Ni alloy, Co alloy, W alloy and the like can be mentioned. When selecting a metal material, it is better to select a metal-based dense coating material, for example, a metal-based self-lubricating composite material, in order to increase the adhesion between the mold material and the coating film.

[0051] A metal-based self-lubricating composite material refers to a metal material matrix containing MoS, WS, BN, and mica. A cermet in which a self-lubricating material that does not easily react with Zr, Ti, Cr, etc., is dispersed and mixed. It has been found that this object can be sufficiently achieved by applying electroless plating, electroplating, or thermal spray coating to a metal material or alloy material as a 铸 -type material. After the coating treatment, the surface of the coating film is preferably smoothed by polishing with about 1000 emery paper.

[0052] The content of the self-lubricating material in the composite material (cermet) to be plated or spray-coated is not particularly limited, but if the content of the self-lubricating material is increased, the reaction resistance and lubricity are improved. Approximately 10-30% by volume is preferable because the peeling resistance of the coating decreases.

[0053] The metal material in the composite material to be plated is not particularly limited, and a metal material or an alloy material can be used. It is preferable to use a metal material and / or an alloy material having a high melting point and a high thermal conductivity. Specific examples include Cu alloy, stainless steel, Ni alloy, Co alloy, W alloy and the like.

[0054] When the Cu alloy is continuously manufactured by the intermittent drawing method of the piece by using the mold of the type (1), (1) the intermittent bow I is at least two orders of magnitude larger than the number of punching cycles. Vibration having a cycle number and a component perpendicular to the drawing direction is applied to the mold, and (2) Continuous supply of lubricant or anti-seizing agent between the inner wall of the mold and the piece. ,of

A greater effect can be obtained by using one or both of V and shift.

[0055] According to the intermittent drawing method of the piece, the frictional resistance between the inner wall of the mold and the piece is reduced, and by improving the lubricity, a sufficiently sound piece can be continuously and efficiently stably obtained. Can be manufactured.

[0056] If a vibration having a cycle number at least two orders of magnitude larger than the number of intermittent drawing cycles and a component perpendicular to the drawing direction is applied to the 铸 type, the same effect can be obtained for a longer time. Can be The frequency is preferably 5000 cpm (83 Hz) or more, more preferably 60,000 cpm (lkHz) or more, which approaches the ultrasonic range.

The lubricant to be supplied between the inner wall of the 铸 type and the 铸 piece is as described above.

(C) A combination of two or more members selected from a self-lubricating material member, a metal-based self-lubricating composite material member, a graphite material member, a ceramic material member, and a metal material member铸 type, and at least the solidification starting position of the molten Cu alloy A continuous structure for a Cu alloy, wherein a self-lubricating material member or a metal-based self-lubricating composite material member is used for a negative inner wall member facing the device.

FIG. 3 is a schematic diagram of a continuous structure for Cu alloy, showing an example of the continuous structure according to the present invention. This is an example in which the mold is composed of a plurality of member members. The mold is composed of a member 3 forming the inner wall of the mold facing the solidification start position 10 of the molten Cu alloy and another member 3 ′ constituting the mold. It is configured. Here, the member 3 constituting the inner wall of the type III facing the solidification start position 10 of the molten Cu alloy is a self-lubricating material member or a metal-based self-lubricating composite material member. For 3 ′, one selected from a graphite material member, a ceramic material member, and a metal material member is used.

[0060] The type II thus constituted by a plurality of member members, that is, the type main body is made of one selected from a graphite material member, a ceramic material member and a metal material member, and Thus, even when the inner wall member of the triangle shape is formed of a self-lubricating material member or a metal-based self-lubricating composite material member, a sound piece can be continuously and efficiently manufactured stably.

[0061] In addition, it is possible to provide a method for continuously producing a Cu alloy, which has excellent fatigue resistance in terms of the properties of the final product after processing and heat treatment, for example, strength, conductivity, and a / !. Particularly when applied to the structure of a Cu alloy containing Zr, Ti, Cr, Ta, V, etc., which are elements that easily form carbides, a great effect can be obtained.

Here, the graphite material member, the ceramic material member, and the metal material member used as the 铸 -shaped main body are all as described above. For the inner wall member of type III, glass-like carbon material, layered carbon material, BN material (Example 22), which are self-lubricating materials, and MoS, WS, BN, mica, etc. Zr, Ti, Cr, etc.

twenty two

Any of a metal-based self-lubricating composite material in which a self-lubricating material that hardly reacts with the metal is dispersed and mixed may be selected.

[0063] (D) A type composed of a combination of two or more members selected from a metal-based self-lubricating composite material member, a graphite material member, a ceramic material member, and a metal material member. Characterized by being coated at least with a に -shaped inner wall 1S self-lubricating material or a metal-based self-lubricating composite material facing the solidification start position of the molten Cu alloy. , Continuous production type for Cu alloy.

FIG. 4 shows an example of a continuous structural mold according to the present invention, which is composed of a plurality of rectangular members, and has a self-lubricating material on the inner wall of the rectangular shape opposite to the solidification start position 10 of the molten Cu alloy. FIG. 3 is a schematic view of a continuous production mold for a Cu alloy provided with a coating 8 of a metal-based self-lubricating composite material. Here, as the member 3 constituting the mold and the other member 3 'constituting the mold, a force is selected from a metal-based self-lubricating composite material member, a graphite material member, a ceramic material member, and a metal material member. Two types of members are used.

[0065] The 铸 -type upstream portion is constituted by one member selected from the group consisting of a graphite material member, a ceramic material member and a metal material member, and the 铸 -type downstream portion is a metal-based self-lubricating composite material member or By using a mold composed of a graphite material and coated with a self-lubricating material or a metal-based self-lubricating composite material on the inner wall of the mold opposite to the solidification start position of the molten Cu alloy In this way, sound chips can be continuously and efficiently produced stably. In addition, it is possible to provide a method for continuously producing a Cu alloy, which is excellent in properties, for example, strength, conductivity, or fatigue strength of a final product after processing and heat treatment. In particular, a great effect can be obtained when applied to the structure of a Cu alloy containing Zr, Ti, Cr, Ta, V, etc., which are elements that easily form carbides.

Here, the graphite material member, the ceramic material member, the metal material member, and the metal-based self-lubricating composite material member used as the 铸 -shaped member are all as described above. In addition, as described above, the coating of the inner wall of the mold 铸 in the matrix of self-lubricating materials such as glassy carbon material, layered carbon material, BN material, and metal material matrix contains MoS, WS, BN,

22 2 Any metal-based self-lubricating composite material in which a self-lubricating material that does not easily react with Zr, Ti, Cr, etc., such as mica, is dispersed and mixed.

(E) The continuous structure for a Cu alloy according to any one of the above (A) to (D), characterized in that a rectangular inner wall facing the molten Cu alloy is coated with a ceramic material.铸 type.

FIG. 5 shows another example of the continuous structure type according to the present invention. In the continuous forming die for a Cu alloy, the member 3 constituting the die including the die portion corresponding to the solidification start position 10 of the molten Cu alloy is formed of a metallic self-lubricating composite material. , Cu alloy The ceramic material is used for the purpose of suppressing the reaction with the molten metal on the inner wall of 铸 type opposite to the molten metal Coating 9 is applied. The coating method of the ceramic material may be any method such as thermal spraying or CVD.

FIG. 6 shows another example of the continuous structure type according to the present invention. In this continuous forming die for Cu alloy, the member 3 constituting the die is formed of a metal material member, and the metal-based self-lubricating composite is formed on the inner wall of the die corresponding to the solidification start position 10 of the Cu alloy melt. A coating 8 of the material is applied, and a coating 9 made of a ceramic material is applied to the inner wall of the 铸 shape facing the molten Cu alloy in order to suppress a reaction with the molten metal. The method of coating the ceramic material is the same as described above.

FIG. 7 shows another example of the continuous structure type according to the present invention. In the continuous forming mold for Cu alloy, the upstream part of the mold is constituted by the metal material member, and the downstream part of the mold is constituted by the graphite material member. The inner wall of the mold is coated with a metal-based self-lubricating composite material 8 and the inner wall of the mold facing the molten copper alloy is coated with a ceramic material 9 to suppress the reaction with the molten metal. Have been. The method of coating the ceramic material is the same as described above.

As shown in FIG. 5-7, when the には -shaped upstream portion is made of a metal material or a metal-based self-lubricating composite material, the reaction between the member and Zr, Ti, Cr, etc. in the molten metal In order to avoid this, it is more effective to coat the ceramic material on the inner wall of the 铸 shape facing the molten Cu alloy. From the standpoint of peeling resistance, as a method of applying ceramics, first coat a cushioning material with a thickness of about 50 / zm (for example, Ni plating, WC-27% by weight NiCr spraying, etc.), and cover it with a 200 m A preferred method is to coat a ceramic spray with a thickness of the order of magnitude. From the viewpoint of reaction resistance, a ceramic material composed of an oxide which is more stable at a production temperature of 1250 ° C of the Cu alloy is preferred.For example, ZrO-8% by weight Y0, ZrO-25% by weight % MgO

2 2 3 2

, ZrO-5% by weight CaO, etc. are recommended because there is no adhesion of the Cu alloy. In addition,

2

It is more preferable to grind a part of the inner wall of the upstream side of the mold to be coated in advance so that no step is formed after coating with ceramics.

According to the present invention, the most effective alloy system is a Cu-Ti-X system (X: Cr, Fe, Co, Ta, Nb, Mo, V, Mn, Be, Si, Ni, Sn, Ag, etc.) , Cu—Zr—X system (X: Cr, Fe, Co, Ta, Nb, Mo , V, Mn, Be, Si, Ni, Sn, Ag, etc.), Cu-Ή-Zr system, etc. Of course, a great effect can be obtained when applied to other alloy systems. In the case of the above component system, there is a cooling process after solidification, as shown by the binary phase diagram of Ti-Cr, Zr-Cr, and Ti-Zr shown in Figs. 8, 9, and 10. In a high temperature range, a Ti-Cr alloy, a Zr-Cr alloy, or metal Ti, metal Zr, or metal Cr is formed. These compounds and metals formed in the high-temperature region where the cooling process occurs after solidification can be solid-solved by subsequent solution treatment, as shown in the phase diagram, which tends to coarsen or agglomerate. It is almost impossible to do.

[0073] The piece obtained by the method of the present invention is not subjected to a hot process such as hot rolling or solution treatment as disclosed in Patent Document 1 described above, and is subjected to rolling at 600 ° C or less. Combination of machining and aging between 150 ° C and 750 ° C can provide significant efficacy only after going through the process to the final product. That is, between Cu and alloying elements, such as Cu Ti and Zr Cu, or

4 9 2

The intermetallic compound between the gold elements or the fine precipitation of metal precipitates such as metal Ti, metal Zr, and metal Cr increases the strength, and thereby solidifies Ti, Zr, Cr, etc., which are harmful to electrical conductivity. It increases the conductivity by reducing the dissolved elements. If a coarse compound or a coarse precipitate exists before the aging treatment, sufficient precipitation hardening cannot be obtained. Also, the presence of these coarse particles reduces the fatigue properties ゃ impact resistance of the final product.

[0074] Since the coarse compound or the coarse precipitate generated in the cooling process after solidification is almost impossible to dissolve, the cooling rate must be increased to prevent the generation. The average cooling rate from the start of solidification to 600 ° C is preferably l ° C / s or more, more preferably 10 ° C / s or more.

[0075] As a Cu alloy to which the present invention is applied, Cr: 0.01-5%, Ti: 0.01-5%, Zr:

0.01-5%, Nb: 0.01-5%, Ta: 0.01-5%, Al: 0.01-5%, Mo: 0.01-5%, V: 0.01-5%, Co: 0.01-5%, Mn: 0.01 Cu alloys containing one or more components selected from —5%, Si: 0.01—5%, Be: 0.01—5%, and Hf: 0.01—15%.

[0076] Alternatively, in addition to these components, at least one group force of the following first to third groups in terms of% by mass may be used in total amount of one or more selected alloy components. There is a Cu alloy containing 0.001-5% by mass.

Group 1: Power of one, two or more selected from P, B, Sb, Bi, Pb, Cd, S and As 0.001-1% by mass

[0077] Alternatively, there is a Cu alloy containing, by mass%, one or more alloy components selected from among Li, Ca, Mg and rare earth elements in a total amount of 0.001-2 mass%. The rare earth elements mean Sc, Y, and lanthanoids, and the raw material of each element may be added to the raw material, or may be added to misch metal.

Prior to the continuous structure using the mold in the method of the present invention, a predetermined Cu alloy is melted. A molten metal having a predetermined chemical composition is formed in a melting furnace lined with a graphite material or the like. It is desirable to perform the dissolving atmosphere in a non-oxidizing atmosphere. When it is necessary to dissolve in the atmosphere, it is effective to use a flux (eg cryolite, fluorite, etc.) or charcoal powder to block the atmosphere. This molten metal is transferred by a ladle to a holding furnace lined with graphite material, alumina bricks and the like.

[0079] In the present continuous structure, any type such as a horizontal type and a vertical type may be used as long as it is a direct connection type continuous structure in which a holding furnace and a mold are directly connected.

Since the type III according to the present invention has low reactivity with molten metal and good lubricity, there are few operational problems when producing the Cu alloy of the present invention. However, the inner wall of the mold near the solidification start position gradually decreases in thickness due to reaction with the molten metal and wear, so that the piece may be hardly pulled out by the pulling force of the piece. In such a case, it is effective to uniformly reduce the thickness by moving the solidification position by adjusting the cooling conditions of the mold, the drawing speed, and the like.

Usually, the piece is intermittently pulled out. (A) Pull-out pattern, (B) Pull-back pattern, (C)

Either a pull-out stop-push-back pattern or (D) a pull-stop-push-back stop-out pattern can be used. However, for the reasons described above, cooling during the cooling process after solidification A higher rejection speed is desirable. In particular, it is desirable to take measures to increase the cooling rate in the secondary cooling zone corresponding to the temperature range where coarse particles are generated. Specifically, water injection, air injection, or air-water mixture injection immediately after leaving the mold is effective, but of course, other methods may be used.

[0080] Thereafter, a combination of processing such as rolling at 600 ° C or lower and aging at 150 to 750 ° C leads to a final product. This processing may, of course, be performed in the cooling process after continuous manufacturing.

Cu alloy containing 2.0 ± 0.1wt% Ti, 1.0 ± 0.1wt% Cr, 0.4 ± 0.02wt% Sn, 0.1 ± 0.01wt% Zn is melted in a high-frequency vacuum melting furnace, and various productions shown in Tables 1 and 2 are performed. Continuous production tests were performed by the method (37 types). The melted Cu alloy melt was transferred to a holding furnace and kept at 1250 ° C., and a piece having a cross section of 20 mm × 200 mm was intermittently extracted under predetermined conditions. Refractories such as melting furnaces or holding furnaces were each made of graphite. The atmosphere during the pouring was air shut off by the Ar gas flow. In each of the tests, a water-cooled cooling chamber made of a Cu alloy was placed on the outside of the mold and the primary cooling was performed, and the piece leaving the mold was subjected to secondary cooling by air-water mixed injection. The temperature was basically measured by using a thermocouple or a radiation thermometer after exiting the 铸 type. For some parts, a through hole was drilled to a position 5 mm outside of the inner wall of the mold and the thermocouple was inserted to measure the mold temperature, and the heat transfer calculation was performed using the physical properties of each mold material. The coagulation start position was estimated. From the above data, the average cooling rate from the start of solidification to 600 ° C was calculated. In the tests shown in Tables 1 and 2, the cooling rate was controlled within the range of 5 ± 2 ° C.

[0082] [Table 1]

table 1

2] table

In addition, the force that aimed to be about 60 m long when the insertion was completed Some of the forces were unusually increased due to the unwinding of the mold due to the initial solidification of the shell, etc. Some have abandoned withdrawal. (4) The quality of one surface was visually judged for flaws. As can be seen from Tables 1 and 2, all of the methods of the present invention were completely successful and the quality was good, but none of the comparative methods could be completed. It was not tolerable.

In exactly the same way as in Example A, a Cu alloy (34 types) having the composition shown in Table 3 was melted and subjected to continuous production tests under different manufacturing conditions, and evaluated in exactly the same manner as in Example A. did. Tables 4 and 5 show the results. In the method of the present invention, good results were obtained for any type, any manufacturing condition, and any chemical composition. On the other hand, in the comparative example in which the type 铸 was changed, the quality was satisfactory and the result was not obtained.

[0086] [Table 3]

Table 3

[0087] [Table 4] s

s

twenty five

s i a

ΐ

a

It is a type II made of a graphite material with a bulk density of 1.82, which targets the alloys shown in Table 6 (three types), and has a cross section of 20 mm X A 200 mm piece was fabricated, the cooling rate from the start of solidification to 600 ° C was varied by changing the amount of water for primary and secondary cooling, and the effect of the cooling rate on the properties was investigated. The cooled pieces are cold rolled to 3 mm, then aged at 400 ° C for 2 hours in an inert gas atmosphere, cold rolled to 0.5 mm again, and finally aged at 350 ° C for 6 hours Processed. The conductivity of the obtained test material and the tensile strength by a tensile test were evaluated by the following methods.

[0090] [Table 6]

[0091] <Tensile strength>

Sample No. 13B specified in JIS Z 2201 was sampled from the above test material, and the tensile strength [TS (MPa)] at room temperature (25 ° C) was determined according to the method specified in JIS Z 2241. Was. [0092] <Conductivity>

A test piece having a width of 10 mm and a length of 60 mm was sampled from the above test material, and a current was passed in the longitudinal direction of the test piece to measure a potential difference between both ends of the test piece, and an electric resistance was obtained by a four-terminal method. Subsequently, the electrical resistance (resistivity) per unit volume was calculated from the volume of the test piece measured with a micrometer, and the specific force with the resistivity of the standard sample annealed with polycrystalline pure copper, 1.72 μΩcm, was also determined by the conductivity [IACS ( %;)].

[0093] If the cooling rate is lower than 0.5 ° C / s, which is the comparative method, cracks occur during cold rolling, and even if cold rolling is performed, the balance between strength and conductivity is poor. On the other hand, the method of the present invention has a good balance between the two, and has a high tensile strength in relation to the electrical conductivity.

[0094] Note that "having a high tensile strength in relation to conductivity" means a state that satisfies the following expression (1). (Hereinafter, this state is referred to as "a state in which the balance between tensile strength and conductivity is good.")

TS≥k + k water exp (-k water IACS) (1)

10 11 12

Where TS: tensile strength (MPa), IACS: conductivity (%),

k = 648.06, k = 985.48, k = 0.0513

10 11 12

In addition, IACS means the percentage with respect to the electrical conductivity of the pure copper polycrystalline material.

[0095] Further, Table 7 shows the results of the same evaluation of the properties of the alloys shown in Table 3 under the above manufacturing conditions, with the cooling rate from the start of solidification to 600 ° C being 5 ° C / s. As a result, all the alloys had a balance between strength and electrical conductivity satisfying the above equation (1), and good results were obtained by the present invention.

[0096] [Table 7]

Table 7

Industrial applicability

The present invention relates to a continuous structure used mainly for a direct connection type continuous structure in which a holding furnace is directly connected to a mold, and a method for continuously manufacturing a Cu alloy using the continuous structure. That is, the present invention provides a mold capable of continuously and efficiently producing a healthy piece, and furthermore, has properties, such as strength and conductivity, or impact resistance, of a final product after processing and heat treatment. It provides a continuous production method for Cu alloys with excellent fatigue strength, and is particularly susceptible to carbide formation./ For the production of Cu alloys containing the elements Zr, Ti, Cr, Ta, V, etc. Big effect when applied can get.

Brief Description of Drawings

FIG. 1 is an example of a continuous fabrication type according to the present invention.

FIG. 2 is an example of a continuous molding type according to the present invention, in which a coating 8 of a self-lubricating material or a metal-based self-lubricating composite material is applied to an inner wall of the type III, which is opposed to a solidification start position of a molten Cu alloy. ing.

FIG. 3 is an example of a continuous forming machine for Cu alloy according to the present invention, which uses a die formed of a plurality of member members.

FIG. 4 is an example of a continuous molding die according to the present invention, which is constituted by a plurality of die members and has a self-lubricating material or metal on an inner wall of the die which is opposed to a solidification start position of a molten Cu alloy. FIG. 1 is a schematic view of a continuous production mold for a Cu alloy provided with a coating 8 of a self-lubricating composite material.

FIG. 5 shows another example of the continuous fabrication type according to the present invention. A coating 9 made of a ceramic material is applied to the inner wall of the rectangular shape opposite to the molten Cu alloy for the purpose of suppressing the reaction with the molten metal.

FIG. 6 shows another example of the continuous structure type according to the present invention. A metal-based self-lubricating composite material coating 8 is applied to the inner wall of the 铸 type opposite to the solidification start position of the molten Cu alloy, and the purpose is to suppress the reaction with the molten metal on the inner wall of the 相対 type facing the molten Cu alloy. A coating 9 of a ceramic material is applied.

FIG. 7 shows another example of the continuous fabrication type according to the present invention. The metal material member constitutes the upstream part of the mold, and the graphite material member constitutes the downstream part of the mold. The metal-based self-lubrication is applied to the inner wall of the mold, which is opposite to the solidification start position of the molten Cu alloy. A coating 8 of a conductive composite material is applied, and a coating 9 made of a ceramic material is applied to the inner wall of the 铸 shape facing the molten Cu alloy for the purpose of suppressing the reaction with the molten metal.

FIG. 8 is a state diagram of a Ti—Cr alloy.

FIG. 9 is a state diagram of a Zr—Cr alloy.

FIG. 10 is a state diagram of a TVZr alloy.

Explanation of reference numerals ： Molten Cu alloy

: Holding furnace wall

： The members that make up the mold

': Other members of the 铸 type

: 铸片

: Cooling chamber

： Secondary cooling

: Pull direction

： Coating on the inner wall of type 鎳 which corresponds to the solidification start position of the molten Cu alloy ： Coating on the inner wall of type 相対 which is opposite to the molten copper alloy

: Solidification start position of molten Cu alloy

Claims

The scope of the claims

[1] Cu is characterized by using a vitreous carbon material, a metal-based self-lubricating composite material, or a graphite material having a bulk density of more than 1.92, at least in the 铸 -shaped portion corresponding to the solidification starting position of the molten Cu alloy. Continuous production type for alloys.

[2] A type III composed of one member selected from a graphite material member, a ceramic material member, and a metal material member or a combination of two or more members, and at least a molten Cu alloy. A continuous production mold for a Cu alloy, characterized in that a mold inner wall facing a solidification start position of the metal is coated with a self-lubricating material or a metal-based self-lubricating composite material.

[3] Composed of two or more members selected from self-lubricating material members, metal-based self-lubricating composite material members, graphite material members, ceramic material members, and metal material members A continuous type for a Cu alloy, wherein a self-lubricating material member or a metal-based self-lubricating composite material member is used as an inner wall member of a 铸 shape at least facing a solidification start position of a molten Cu alloy. Manufacturing type.

[4] Composed of two or more members selected from self-lubricating material members, metal-based self-lubricating composite material members, graphite material members, ceramic material members, and metal material members A continuous type for a Cu alloy, wherein the inner wall of the 壁 type, which is at least the solidification start position of the molten Cu alloy, is coated with a self-lubricating material or a metal-based self-lubricating composite material. Manufacturing type.

[5] The continuous structure for a Cu alloy according to any one of claims 1 to 4, wherein the inner wall of the mold corresponding to the molten Cu alloy is coated with a ceramic material.

[6] A method for continuously producing a Cu alloy, comprising continuously producing the mold according to any one of claims 1 to 5 by an intermittent drawing method of a piece.

[7] In the case of continuous production of Cu alloy by the intermittent drawing method of the piece, the intermittent bow of the piece has at least two orders of magnitude greater than the number of cycles and the number of cycles, and is perpendicular to the drawing direction. A continuous production method for Cu alloys, characterized by imparting vibrations having various components to the mold.

[8] When continuously forming a Cu alloy by the intermittent drawing method of a piece, the inner wall of Characterized by continuously supplying a lubricant or an anti-seizure agent between the pieces.

Continuous production method of Cu alloy.

[9] In the case of continuous production of Cu alloy by the intermittent drawing method of the piece, the intermittent bow of the piece has at least two orders of magnitude greater than the number of cycles of punching, and is perpendicular to the drawing direction. A method for continuously producing a Cu alloy, comprising: applying vibration having various components to a mold; and continuously supplying a lubricant or an anti-seizure agent between an inner wall of the mold and a piece.

[10] In the continuous production of Cu alloy by the intermittent drawing method of the piece, the intermittent bow of the piece has at least two orders of magnitude greater than the number of cycles and the number of cycles, and is perpendicular to the drawing direction. 7. The method for continuously producing a Cu alloy according to claim 6, wherein a vibration having various components is applied to the mold.

[11] A claim characterized by continuously supplying a lubricant or an anti-seizure agent between the inner wall of the mold and the piece when the Cu alloy is continuously produced by the intermittent drawing method of the piece. Item 11. The method for continuously producing a Cu alloy according to item 6 or 10.

In [12] Cu alloy strength by weight ^{_{0/0, Cr: 0.01-5%}} , Ti: 0.01-5%, Zr: 0.01-5%, Nb: 0.01- 5%, Ta: 0.01 one 5%, Al: 0.01 5%, Mo: 0.01—5%, V: 0.01—5%, Co: 0.01—5%, Mn: 0.01—5%, Si: 0.01—5%, Be: 0.01—5%, and Hf: 0.01— The method for continuously producing a Cu alloy according to any one of claims 6 to 11, comprising one or more components selected from among 5%.

[13] The Cu alloy further contains, in mass%, at least one of the following first group forces of the group up to the third group: one or more selected alloy components in a total amount of 0.001- 13. The method for continuously producing a Cu alloy according to claim 12, wherein the content is 5% by mass.

Group 3: One or two selected from among Te, Se, Sr, Tl, Rb, Cs, Ba, Re, Os, Rh, Po, Ga, Tc, Ru, Pd, Ir, Pt and Ta Above total 0.01-3% by mass [14] Cu alloy strength Further, it is characterized in that it contains 0.001-2 mass% in total of one or more alloy components selected from Li, Ca, Mg and rare earth elements in mass%. 14. The method for continuously producing a Cu alloy according to claim 12 or 13.