KR20210080520A - A titanium alloy plate, a manufacturing method of a titanium alloy plate, a copper foil manufacturing drum, and a manufacturing method of a copper foil manufacturing drum - Google Patents

Abstract

This titanium alloy plate is, in mass%, Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0% or less 1 type or 2 types or more comprised from the group consisting of: 0.2% or more and 7.0% or less in total, N: 0.100% or less, C: 0.080% or less, H: 0.015% or less, O: 0.700% or less, and Fe: 0.500% or less, and the balance contains Ti and impurities It has a chemical composition, the average crystal grain size is 40 μm or less, the standard deviation of the particle size distribution based on the logarithm of the crystal grain size (μm) is 0.80 or less, the crystal structure includes an α phase having a hexagonal closest packing structure, and the plate thickness The area ratio of the crystal grains in which the angle formed by the [0001] direction of the α phase with respect to the direction is 0° or more and 40° or less is 70% or more.

Description

A titanium alloy plate, a manufacturing method of a titanium alloy plate, a copper foil manufacturing drum, and a manufacturing method of a copper foil manufacturing drum

The present invention relates to a titanium alloy plate, a method for manufacturing a titanium alloy plate, a copper foil manufacturing drum, and a manufacturing method for a copper foil manufacturing drum.

This application claims priority on the basis of Japanese Patent Application No. 2019-078824, filed in Japan on April 17, 2019 and Japanese Patent Application No. 2019-078828, filed in Japan on April 17, 2019, , his contents are cited here.

In most cases, copper foil is used as a raw material for the wiring of wiring boards, such as a multilayer wiring board and a flexible wiring board, and the electrically-conductive site|part of electronic components, such as a collector of a lithium ion battery.

The copper foil used for such a use is manufactured with the copper foil manufacturing apparatus provided with a copper foil manufacturing drum. 7 : is a schematic diagram of a copper foil manufacturing apparatus. The copper foil manufacturing apparatus 1 is, for example, as shown in FIG. 7, the electrolytic cell 10 in which the copper sulfate solution is stored, and the electrodeposition drum 2 provided in the electrolytic cell 10 so that a part may be immersed in the copper sulfate solution. and an electrode plate 30 immersed in a copper sulfate solution in the electrolytic cell 10 to face the outer peripheral surface of the electrodeposition drum 2 at a predetermined interval. By applying a voltage between the electrodeposition drum 2 and the electrode plate 30 , the copper foil A is electrodeposited and produced on the outer peripheral surface of the electrodeposition drum 2 . Copper foil A having a predetermined thickness is peeled off from the electrodeposition drum 2 by the winding unit 40 and is wound around the winding roll 60 while being guided by the guide roll 50 .

As a material of a drum (electrodeposition drum), titanium is generally used for the surface (outer peripheral surface) from a viewpoint of being excellent in corrosion resistance, being excellent in the peelability of copper foil, etc. However, even when a titanium material excellent in corrosion resistance is used, when the copper foil is manufactured over a long period of time, the surface of the titanium material constituting the drum is gradually corroded in the copper sulfate solution. And, the state of the surface of the drum subjected to corrosion may be transferred to the copper foil during the manufacture of the copper foil.

It is known that corrosion of a metal material differs in the state of corrosion and the degree of corrosion depending on various internal factors resulting from the metal structure, such as the crystal structure, crystal orientation, defects, segregation, processing strain, and residual strain of the metal material. When a drum using a metal material having a heterogeneous metal structure between parts is corroded along with the production of copper foil, the drum cannot maintain a homogeneous surface state, resulting in a non-uniform surface on the drum surface. Any irregularities on the drum surface can be identified by the shape. Among the patterns resulting from such a heterogeneous metal structure, a pattern that can be visually recognized due to a macro structure having a relatively large area is called a "macro pattern". The macro pattern generated on the drum surface can be transferred to the copper foil during the production of the copper foil.

Therefore, in order to manufacture a copper foil with high precision and a homogeneous thickness, the macro structure of the titanium material constituting the drum is made homogeneous, and the corrosion of the surface of the drum is made homogeneous, so that the macro shape resulting from the heterogeneous macro structure is made. It is important to reduce

Patent Document 1 contains, in mass%, Cu: 0.15% or more and less than 0.5%, oxygen: more than 0.05%, 0.20% or less, and Fe: 0.04% or less, and the balance consists of titanium and unavoidable impurities, and the average grain size A titanium plate for an electrolytic Cu foil manufacturing drum has been proposed, characterized in that it contains an α-phase homogeneous fine recrystallized structure of less than 35 µm.

Patent Document 2 contains, in mass%, Cu: 0.3 to 1.1%, Fe: 0.04% or less, oxygen: 0.1% or less, hydrogen: 0.006% or less, and has an average grain size of 8.2 or more, and a Vickers hardness of 115 More than or less than 145, in a portion parallel to the plate surface, the texture is the (0001) plane pole figure of the α phase from the normal direction (ND axis) to the rolling plane, the collapse angle of the normal to the (0001) plane is , the total area of crystal grains existing within the range of an ellipse with ±45° as the major axis in the rolling width direction TD direction and ±25° as the minor axis in the final rolling direction RD direction is A, and the total area of other crystal grains is B, , A titanium plate for an electrolytic Cu foil manufacturing drum, characterized in that the area ratio A/B is 3.0 or more, is proposed.

Patent Document 3 contains Al: 0.4 to 1.8%, and has an average grain size of 8.2 or more and Vickers hardness of 115 or more and 145 in a portion parallel to the plate surface at a plate thickness of 4 mm or more, 1.0 mm below the surface and 1/2 plate thickness. Hereinafter, in the portion parallel to the plate surface from 1 mm below the surface to 1/2 plate thickness, the texture is the final rolling direction RD, the normal to the rolling surface, ND the rolling width direction, and the normal to the TD (0001) plane is the c-axis. In the (0001) plane pole figure of the α phase from the normal direction on the rolling surface, the angle of collapse of the c-axis in the TD direction is -45 to 45°, and the angle of collapse of the c-axis in the RD direction is -25 to 25° A titanium alloy thick plate having an area ratio A/B of 3.0 or more is proposed, in which A is the total area of the crystal grains having the c-axis in the phosphor ellipse region, and B is the total area of the other crystal grains.

In Patent Document 4, when manufacturing titanium and titanium alloy plates by a method including a step of sequentially performing ingot forging, rough hot rolling, and finish hot rolling, the heating temperature in ingot forging and rough hot rolling is set to 950 ° C. or higher At the same time, the heating temperature in finish hot rolling is set to 700° C. or less, and cross hot rolling is performed in which the rolling directions of rough hot rolling and finish hot rolling are changed. Titanium and titanium alloy having a uniform fine macro shape A method for manufacturing a plate has been proposed.

Patent Document 5 discloses a cathode electrode made of titanium containing a titanium material used when obtaining an electrolytic copper foil using a copper electrolyte, wherein the titanium material has a crystal grain size number of 7.0 or more and an initial hydrogen content of 35 ppm or less, characterized in that A cathode electrode made of titanium for producing an electrolytic copper foil has been proposed. In Patent Document 5, when this cathode electrode made of titanium is used, compared with the prior art, it can be used for a very long time in the production of an electrolytic copper foil, the number of maintenance can be effectively reduced, and a high-quality electrolytic copper foil can be maintained over a long period of time. It is disclosed that it becomes possible to manufacture.

Patent Document 6 contains, in mass%, Cu: 0.5 to 2.1%, Ru: 0.05 to 1.00%, Fe: 0.04% or less, and oxygen: 0.10% or less, the remainder being titanium and unavoidable impurities, and homogeneous fine recrystallization A titanium plate for an electrolytic Cu foil manufacturing drum has been proposed, which has a structure.

However, further thinning and improvement of surface quality are calculated|required by copper foil with size reduction and density increase of this electronic component. Under these circumstances, further reduction of the macro pattern described above is demanded. In the prior art described in Patent Documents 1 to 6, the macro pattern could not be sufficiently reduced.

In addition, since the drum used for manufacturing copper foil is manufactured by shrink-fitting a plate of insoluble metal, such as a titanium plate, to the surface of the core material used as the core of a copper foil manufacturing drum, from a viewpoint of productivity of a copper foil manufacturing drum, , it is preferable that the plate to be shrink-fitted to the surface of the core material is a plate excellent in shrink-fitting property.

However, in the techniques of Patent Documents 1 to 6, labor is required for the shrink fit operation between the core material and the titanium plate, and there is room for improvement in the productivity of the copper foil manufacturing drum.

In addition, in addition to being manufactured by ring forging, the copper foil manufacturing drum mentioned above is manufactured by bending a titanium plate into cylindrical shape, and welding the adjacent edge part. The latter method is suitable for manufacturing a high-quality copper foil manufacturing drum from a point which is easy to control the metal structure of a titanium plate. By making the macro structure of the titanium material which comprises a copper foil manufacturing drum homogeneous and achieving homogeneous corrosion of a drum, the macro pattern resulting from the heterogeneous macro structure can be reduced. However, with respect to the welded part of the drum manufactured by welding, since the metal structure is unavoidably different from that of other parts, even if the macro structure of the titanium material used as the surface material of the copper foil manufacturing drum is made homogeneous, the macro resulting from the welded part is There was a problem that the shape was easy to produce.

Although the ratio of the welding part in the surface of a copper foil manufacturing drum is not large, the request|requirement with respect to reduction of the macro pattern of a welding part is increasing in recent years.

Regarding welding of titanium materials, Patent Document 7 discloses a Ti-based wire rod for forming molten metal having a predetermined tensile strength in the longitudinal direction of the wire rod and having a Ti-based oxide film having a thickness of 1 µm or more and 5 µm or less on the surface of the wire rod body. is proposed. Further, Patent Document 8 proposes a welding wire made of Ti or a Ti alloy having an oxygen concentrating layer on the surface and a metal compound having at least one metal selected from the group of alkali metals and alkaline earth metals. .

However, the technique described in patent documents 7 and 8 is not for improving the structure|tissue of the welding in manufacture of a copper foil manufacture titanium drum, and a welded part. Therefore, it is difficult to suppress the macro pattern using the same technique. That is, the titanium bar material for welding which is used in manufacture of the titanium drum made from copper foil and can suppress generation|occurrence|production of the macro pattern in the welding part of the titanium drum made from copper foil has not been fully investigated conventionally.

Japanese Patent Laid-Open No. 2009-41064 Japanese Patent Laid-Open No. 2012-112017 Japanese Patent Laid-Open No. 2013-7063 Japanese Patent Laid-Open No. 60-9866 Japanese Patent Laid-Open No. 2002-194585 Japanese Patent Laid-Open No. 2005-298853 Japanese Patent Laid-Open No. 2005-21983 Japanese Patent Laid-Open No. 2006-291267

The present invention has been made in view of the above problems, and an object of the present invention is to manufacture a copper foil manufactured using a titanium alloy plate and a copper titanium alloy plate that can suppress the occurrence of macro patterns when used in a drum for copper foil production To provide drums.

In addition, a preferred object of the present invention is to suppress the occurrence of macro patterns when used in a drum for manufacturing copper foil, and also to produce a titanium alloy plate and copper foil manufactured using a copper titanium alloy plate having excellent shrink fit. To provide drums.

Moreover, the other preferable object of this invention is copper foil manufacture using the titanium wire for welding which is used in manufacture of the copper foil manufacture titanium drum, and can suppress the generation|occurrence|production of the macro pattern in the welding part of the copper foil manufacture titanium drum. It is to provide a drum manufacturing method and a copper foil manufacturing drum.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the above-mentioned problem. As a result, only by reducing the grain size of the texture in the titanium material or making the normal of the (0001) surface of the crystal perpendicular to the rolling surface (plate surface), the generation of macro shapes can be reduced to the required level this time. I found out what I couldn't control.

As a result of examination by the present inventors again, the chemical composition is a chemical composition in which the precipitation of the β phase is suppressed, and in the structure, the crystal grains are made not only fine but also of a uniform size, and the crystal structure is a hexagonal closest packed structure α Including the phase, the area ratio of crystal grains in which the angle formed in the [0001] direction (c-axis) of the α phase with respect to the plate thickness direction is 0° or more and 40° or less is 70% or more, preferably further in the normal direction of the plate surface In the (0001) pole figure from (0001), the peak of the degree of integration of the crystal grains exists within 30° from the normal direction of the plate surface, and by controlling so that the maximum degree of integration is 4.0 or more, it is possible to suppress the occurrence of macro shapes. found out that there is And the manufacturing method of the titanium alloy plate which can achieve such a chemical composition and texture at the same time was discovered, and it led to this invention.

Moreover, the present inventors examined also the shrink fit property of the titanium alloy plate to a core material in manufacture of a copper foil manufacturing drum. As a result, it was found that the Young's modulus of the titanium alloy sheet affects the shrink fit property.

Based on this knowledge, the present inventors studied paying attention to the hardness of a titanium alloy plate, a crystal grain size, a crystal orientation, a 2nd phase, and distribution of an element. As a result, when Al is contained in a larger amount than the titanium alloy plate used for a general copper foil manufacturing drum, grain growth is suppressed and a microstructure is easily formed, the hardness of the titanium alloy plate becomes large, and the Young's modulus of the titanium alloy plate is found to improve.

Moreover, the present inventors examined suppression of the generation|occurrence|production of the macro pattern in a welding part. As a result, it discovered that it was possible to suppress generation|occurrence|production of the macro pattern in a weld part making the metal structure of a weld part mainly alpha, and controlling hardness while refine|miniaturizing a crystal grain. In addition, in order to obtain the structure of such a welded part, it was found that it is effective to make the titanium wire for welding contain at least one selected from the group consisting of Sn, Zr, and Al and O in an appropriate amount.

The summary of this invention completed based on the said knowledge is as follows.

[1] The titanium alloy plate according to one aspect of the present invention, in mass%, is selected from the group consisting of Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0% or less. One or two or more constituents: 0.2% or more and 7.0% or less in total, N: 0.100% or less, C: 0.080% or less, H: 0.015% or less, O: 0.700% or less, and Fe: 0.500% or less and the balance has a chemical composition containing Ti and impurities, the average grain size is 40 µm or less, the standard deviation of the grain size distribution based on the logarithm of the grain size in unit µm is 0.80 or less, and the crystal structure is hexagonal closest packing The area ratio of the crystal grains including the α phase as a structure and having an angle between the [0001] direction of the α phase with respect to the plate thickness direction of 0° or more and 40° or less is 70% or more.

[2] In the titanium alloy plate described in [1] above, in the (0001) pole figure from the normal direction of the plate surface, the expansion index of the pole figure using the spherical harmonic function method of the electron beam backscattering diffraction method is 16, the Gaussian half value The peak of integration calculated by texture analysis when the width is 5° exists within 30° from the normal direction of the plate surface, and the maximum integration degree may have a texture of 4.0 or more.

[3] In the titanium alloy sheet according to [1] or [2], the standard deviation of the particle size distribution may be (0.35×lnD-0.42) or less when the average crystal grain size is D in unit μm.

[4] In the titanium alloy plate according to any one of [1] to [3], when the cross section in the plate thickness direction is observed, the total grain boundary length of the plate thickness section at the position of 1/4 plate thickness from the surface is The ratio of the length of the twin grain boundary to each other may be 5.0% or less.

[5] The titanium alloy plate according to any one of [1] to [4], wherein, in the chemical composition, Sn: 0.2% or more and 2.0% or less, Zr: 0.2% or more and 5.0% or less, and Al: 0.2% or more You may contain 0.2 % or more and 5.0 % or less of 1 type, or 2 or more types comprised from the group which consists of 3.0 % or less in total.

[6] The titanium alloy plate according to any one of [1] to [4] above contains Al: more than 1.8% and 7.0% or less in the chemical composition, and may have a Vickers hardness of 350 Hv or less.

[7] In the titanium alloy plate described in [6] above, the Al content by mass% is [Al%], the Zr content is [Zr%], the Sn content is [Sn%], and the O content is [0%] , the Al equivalent Aleq represented by the following formula (1) may be 7.0 or less.

Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1)

[8] The titanium alloy plate according to the above [6] or [7], using an electron beam microanalyzer, a surface perpendicular to the plate thickness direction at a position of 1/4 plate thickness from the surface 20 mm x 20 mm or more When the analysis region was compositionally analyzed, the average Al content was [Al%], and the concentration of Al with respect to the area of the analysis region was ([Al%]-0.2) mass% or more [Al%]+0.2) mass The area ratio of the area|region which is % or less may be 90 % or more.

[9] The titanium alloy plate according to any one of [1] to [8] above may contain the α phase in an amount of 98.0% by volume or more.

[10] The titanium alloy plate according to any one of [1] to [9] may be a titanium alloy plate for a copper foil production drum.

[11] A copper foil production drum according to another aspect of the present invention includes a cylindrical inner drum, the titanium alloy plate according to any one of [1] to [10], the titanium alloy plate being deposited on the outer peripheral surface of the inner drum, and the titanium It has a weld provided in the butt|matching part of an alloy plate, the metal structure of the said weld part has 98.0% or more of alpha phases by volume ratio, It is a particle size number based on JISG0551:2013, and is 6 or more and 11 or less.

[12] The manufacturing method of the copper foil manufacturing drum which concerns on another aspect of this invention has a welding process of welding two adjacent ends of the titanium alloy plate processed into cylindrical shape using the titanium wire for welding, Titanium wire for welding, in mass%, at least one selected from the group consisting of Sn, Zr and Al: 0.2% or more and 6.0% or less in total, O: 0.01% or more and 0.70% or less, N: 0.100% or less, C : 0.080% or less, H: 0.015% or less, and Fe: 0.500% or less, and the balance has a chemical composition containing Ti and impurities.

[13] In the method for manufacturing a copper foil manufacturing drum according to [12], in the titanium wire for welding, at least a part of O is at least one element selected from the group consisting of Ti, Sn, Zr and Al. may exist as an oxide of

According to the said aspect of this invention, when it uses for the drum for copper foil manufacturing, it becomes possible to provide the copper foil manufacturing drum manufactured using the titanium alloy plate and copper titanium alloy plate which can suppress generation|occurrence|production of a macro pattern. .

Moreover, according to the preferable aspect of this invention, when it uses for the drum for copper foil manufacture, generation|occurrence|production of a macro pattern can be suppressed and it becomes possible to provide the titanium alloy plate excellent in shrink fit property.

Moreover, according to the preferable aspect of this invention, it becomes possible to provide the manufacturing method and copper foil manufacturing drum of the copper foil manufacturing drum which suppress generation|occurrence|production of the macro pattern in the welding part of a copper foil manufacturing drum.

BRIEF DESCRIPTION OF THE DRAWINGS It is an example of the (0001) pole figure from the normal line direction (ND) in the rolling surface of the titanium alloy plate which concerns on one Embodiment of this invention.
2 is a photomicrograph showing an example of a macro pattern observed on the surface of a titanium alloy plate after corrosion.
3 is a reference diagram emphasizing the macro shape in order to indicate the position of the macro shape.
It is explanatory drawing for demonstrating the crystal orientation of the alpha phase.
5 is an example of a crystal orientation map showing an example of crystal orientation analysis.
It is explanatory drawing of the (0001) pole figure from the normal line direction (ND) of a rolling surface for demonstrating the crystal orientation of the titanium alloy plate which concerns on one Embodiment of this invention.
It is a schematic diagram of a copper foil manufacturing apparatus.
It is a schematic diagram of the copper foil manufacturing drum which concerns on this embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail.

<1. Titanium alloy plate>

First, the titanium alloy plate which concerns on this embodiment is demonstrated. It is assumed that the titanium alloy plate which concerns on this embodiment is used as a material of the drum for copper foil manufacture (copper foil manufacture drum). Therefore, the titanium alloy plate which concerns on this embodiment can also be called the titanium alloy plate for copper foil manufacturing drums. When used in a copper foil manufacturing drum, one side of a titanium alloy plate comprises the cylindrical surface of a drum.

(1.1 chemical composition)

First, the chemical composition of the titanium alloy plate which concerns on this embodiment is demonstrated. The titanium alloy plate according to the present embodiment is, by mass%, Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0% or less, one type or Two or more types contain a total of 0.2% or more and 7.0% or less, N: 0.100% or less, C: 0.080% or less, H: 0.015% or less, O: 0.700% or less, and Fe: 0.500% or less, the balance being Ti and impurities. Hereinafter, unless otherwise specified, the expression of "%" regarding a chemical composition shall indicate "mass %".

Industrial pure titanium contains very small amounts of additive elements, and the structure is substantially α-phase, single-phase. When such a titanium alloy plate made of industrial pure titanium is used for the drum, the drum is uniformly corroded when the drum is immersed in a copper sulfate solution. Thereby, the generation|occurrence|production of the macro pattern by the difference in the corrosion rate of alpha phase and beta phase is suppressed.

The titanium alloy plate according to the present embodiment is substantially α-phase single-phase industrial pure titanium, in mass%, Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0 It is an alloy plate contained so that 1 type or 2 or more types comprised from the group which consists of % or less may become 0.2% or more and 7.0% or less in total.

The reason for limitation of content of each element is demonstrated.

<Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0% or less: one or two or more types: 0.2% or more and 7.0% or less in total>

When the total content of one or two or more selected from the group consisting of Sn, Zr, and Al is 0.2% or more, crystal grain growth can be stably suppressed.

On the other hand, when the total content of one or two or more types selected from the group consisting of Sn, Zr and Al is 7.0% or less, the above-described high-temperature strength of the titanium alloy sheet after hot rolling does not occur. From the viewpoint of high-temperature strength, preferably, the Al content is 0.2% or more and 3.0% or less, and the total content of one or two or more selected from the group consisting of Sn, Zr and Al is 0.5% or more and 5.0% or less to be. The sum total of the 1 type(s) or 2 or more types of content chosen from the group which consists of Sn, Zr, and Al becomes more preferably 0.5 % or more and 4.0 % or less.

Sn is a neutral element and is an element which suppresses crystal grain growth by solid solution in titanium. When Sn content is 0.2 % or more, crystal grain growth can be suppressed stably. Therefore, Sn content becomes like this. Preferably it is 0.2 % or more. The Sn content is more preferably 0.3% or more.

In addition, Sn stabilizes each phase by solid solution in the α phase and the β phase in titanium. When there is too much Sn content, high temperature intensity|strength will become high, and the plate shape after hot rolling will deform|transform by the reaction force at the time of hot rolling, and it will become easy to become a wave shape. A dislocation is introduced into the crystal of the titanium alloy plate by applying a strain to the wavy titanium alloy plate by processing for correcting the shape. This dislocation becomes a cause, and a macro pattern becomes easy to generate|occur|produce. Moreover, when there is too much Sn content, the toughness of a titanium alloy plate will become small, the shrink fit property at the time of copper foil manufacturing drum manufacture will fall, and productivity will fall. Therefore, it is preferable that Sn content is 2.0 % or less, More preferably, it is 1.5 % or less. Since Sn is not essential in a titanium alloy plate, when Zr and/or Al are contained 0.2% or more in total, 0% of Sn content may be sufficient.

Zr is a neutral element like Sn, and is an element which suppresses crystal grain growth by solid solution in titanium. When the Zr content is 0.2% or more, crystal grain growth can be stably suppressed. Therefore, Zr content becomes like this. Preferably it is 0.2 % or more. The Zr content is more preferably 0.3% or more.

On the other hand, Zr is an element that stabilizes each phase by solid solution in the α phase and the β phase in titanium. When the Zr content is too large, the two phases of the α phase and the β phase are thermally stable and the existing temperature range is widened, and the β phase tends to precipitate during heating. Since the β phase corrodes preferentially over the α phase, when a drum having a titanium alloy plate containing the β phase on its surface is used for production of copper foil, the β phase preferentially corrodes and a macro pattern is formed on the drum surface. As a result, there is a possibility that the macro pattern is transferred to the copper foil. Moreover, a strength difference arises between the parts of a titanium alloy plate by solidification segregation, and when the obtained titanium alloy plate is grind|polished, a macro pattern generate|occur|produces. Therefore, the Zr content is 5.0% or less. Zr content becomes like this. Preferably it is 4.5 % or less, More preferably, it is 4.0 %. Zr content becomes like this. More preferably, it is 2.5 % or less, More preferably, it is 2.0 % or less. Since Zr is not essential in a titanium alloy plate, when Sn and/or Al are contained 0.2% or more in total, 0% of Zr content may be sufficient.

Al is an α-phase stabilizing element, and in the heat treatment in the temperature region of the α-phase single phase, similarly to Sn and Zr, grain growth is suppressed. When Al content is 0.2 % or more, crystal grain growth can be suppressed stably. Therefore, the Al content is preferably 0.2% or more. The Al content is more preferably 0.5% or more.

Moreover, Al is also an element which increases the Young's modulus of a titanium alloy plate. By increasing the Young's modulus, the shrink fit property when the core material and the titanium alloy plate are shrink-fitted in the production of the copper foil production drum is improved. Thereby, the productivity of a copper foil manufacturing drum improves. In addition, by increasing the Young's modulus, it is uniformly shrink-fitted and the abrasiveness of the titanium alloy plate is improved. As a result, it also becomes possible to suppress the occurrence of macro patterns.

From the viewpoint of increasing the Young's modulus and improving the shrink fit property, it is preferable that the Al content be more than 1.8%.

On the other hand, Al increases the high temperature strength of a titanium alloy plate more compared with Sn or Zr. As mentioned later, when manufacturing the titanium alloy plate which concerns on this embodiment, for the purpose of texture control, hot rolling is performed to comparatively low temperature. Therefore, when high temperature intensity|strength becomes high too much, the reaction force at the time of hot rolling will become large, the shape of the titanium alloy plate after hot rolling will deform|transform large, and a titanium alloy plate will become corrugated. Therefore, although many subsequent corrections are needed with respect to a titanium alloy plate, when a deformation|transformation is provided at that time, many dislocations will be introduce|transduced. As a result, when a titanium alloy plate is used for a drum, it becomes easy to generate|occur|produce a macro pattern. When the Al content is more than 7.0%, toughness and workability decrease, making drum manufacturing difficult. As a result, the productivity of a copper foil manufacturing drum falls. Therefore, the Al content is made 7.0% or less. From the said viewpoint, it is preferable to set it as 3.0 % or less, and, as for Al content, it is more preferable to set it as 2.5 % or less. Since Al is not essential in a titanium alloy plate, when Sn and/or Zr are contained 0.2% or more in total, 0% of Al content may be sufficient.

Moreover, when Al content is high, there is a concern that segregation occurs in Al. When segregation occurs in Al, a difference in hardness and electrical resistance occurs between portions of the titanium alloy plate. As for the titanium alloy plate in which the fluctuation|variation arose in hardness, large unevenness|corrugation may be formed in the titanium alloy plate at the time of grinding|polishing, and a macro pattern may generate|occur|produce. Moreover, a difference in corrosion rate may arise by the fluctuation|variation in electrical resistance, and a macro pattern may generate|occur|produce. Therefore, the smaller Al concentration distribution is good.

In the titanium alloy plate according to the present embodiment, when the Al content is more than 1.8%, the Al content (average content) is [Al%], the concentration of Al is ([Al%] -0.2) mass% It is preferable that the area ratio of the area|region of more than [Al%]+0.2) mass % is 90 % or more. Thereby, a macro pattern can be suppressed stably.

The Al segregation was evaluated by using an electron probe microanalyzer (EPMA) with a beam diameter of 500 µm and a step size of 500 µm equal to the beam diameter, and the plate thickness from the surface perpendicular to the plate thickness direction. It is carried out by composition analysis of an area of 20 mm x 20 mm or more in the position of 1/4 of the . In order to convert the composition analysis result into alloy element concentration, the average chemical composition of JIS Class 1 industrial pure titanium and the target titanium alloy plate and the intensity of Kα ray are analyzed, and a calibration curve obtained by linear approximation from the result is used.

Moreover, in the titanium alloy plate which concerns on this embodiment, Al content is [Al%] (mass %), Zr content is [Zr%] (mass %), Sn content is [Sn%] (mass %), O content It is preferable that Al equivalent Aleq represented by following formula (1) is 7.0 (mass %) or less when [0%] (mass %) is made into [0%] (mass %).

Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1)

The Al equivalent is an index indicating the degree of stabilization of the α phase, and as the Al equivalent increases, the hardness increases while the toughness decreases. When the Al equivalent is 7.0% by mass or less, toughness can be maintained and shrink fit property can be improved.

<O: 0.700% or less>

O is an element which contributes to the improvement of the intensity|strength of a titanium alloy plate, and contributes to the increase of surface hardness. However, when the strength of the titanium alloy sheet becomes too high, relatively large processing is required at the time of forcing, and twin crystals are likely to occur. Moreover, when surface hardness becomes large too much, when a titanium alloy plate is used as a drum, grinding|polishing will become difficult. Therefore, when O is contained in a titanium alloy plate, O content shall be 0.700 % or less. The O content is preferably 0.400% or less. O content becomes like this. More preferably, it is 0.150 % or less, More preferably, it is 0.120 % or less. Since O is not essential in a titanium alloy plate, the lower limit of the content is 0 %. However, it is difficult to prevent contamination from sponge titanium as a melting raw material or an additive element, and the practical lower limit is 0.020%.

When the strength improvement effect is obtained by the O content, the O content is preferably 0.030% or more.

<Fe: 0.500% or less>

Fe is an element that strengthens the β phase. In a titanium alloy plate, since generation|occurrence|production of a macro pattern will be affected when the precipitation amount of β phase increases, when Fe is contained in a titanium alloy plate, the upper limit of Fe content shall be 0.500 %. Fe content becomes like this. Preferably it is 0.100 % or less, More preferably, it is 0.080 % or less. Since Fe is not essential in a titanium alloy plate, the minimum of the content is 0 %. However, in actual production, it is difficult to prevent the mixing of Fe, and the practical lower limit is 0.001%.

<N: 0.100% or less>

<C: 0.080% or less>

<H: 0.015% or less>

The titanium alloy plate according to the present embodiment may further contain N, C, or H as an impurity.

N is an element which forms a nitride with Ti. When a nitride is formed, a titanium alloy plate may harden or become embrittled. Therefore, it is preferable to suppress the content of N as much as possible. In the titanium alloy plate which concerns on this embodiment, N content shall be 0.100 % or less. The N content is preferably 0.080% or less. Since N is not essential in a titanium alloy plate, the lower limit of the content is 0 %. However, N is an impurity mixed in the manufacturing process, and it is good also considering the lower limit of a substantial N content as 0.0001%.

C is an element which forms a carbide with Ti and hardens or embrittles a titanium alloy plate similarly to a nitride. In order to suppress hardening and embrittlement of a titanium alloy plate, it is preferable to make C content as low as possible. In the titanium alloy plate which concerns on this embodiment, C content shall be 0.080 % or less. The C content is preferably 0.050% or less. Since C is not essential in a titanium alloy plate, the lower limit of the content is 0 %. However, C is an impurity mixed in during the manufacturing process, and the lower limit of the substantial C content may be set to 0.0005%.

H is an element which forms a hydride with Ti. When a hydride is formed, a titanium alloy plate may become embrittled. Moreover, a macro pattern may generate|occur|produce by a hydride. Therefore, it is preferable to suppress the H content as much as possible. In the titanium alloy plate which concerns on this embodiment, H content shall be 0.015 % or less. The H content is preferably 0.010% or less. Since H is not essential in a titanium alloy plate, the lower limit of the content is 0 %. However, H is an impurity mixed in during the manufacturing process, and the lower limit of the substantial H content may be set to 0.0005%.

Remainder of the chemical composition of the titanium alloy plate which concerns on this embodiment contains Ti and an impurity, and may consist of Ti and an impurity. In addition to the above-mentioned elements, if specifically exemplified, the impurities include Cl, Na, Mg, Si, Ca, and Mo, Nb, Ta, V, Cr, Mn, Co, Ni, Cu, etc. mixed from scrap. . There is no problem with impurities as long as the total content is 0.50% or less.

However, the impurity may include a β-phase stabilizing element. If the amount of the β-phase precipitation increases, the occurrence of macro patterns is affected, so the amount of the β-phase stabilizing element is preferably small. Examples of the β-phase stabilizing element include V, Mo, Ta, Nb, Cr, Mn, Co, Ni, and Cu. In the titanium alloy plate which concerns on this embodiment, in addition to having made content of an impurity into 0.50 % or less in total, it is more preferable that content of each beta-phase stabilizing element contained in a titanium alloy plate is 0.10 % or less.

A chemical composition is calculated|required with the following method.

β-stabilizing elements such as Al, Zr, Sn, Fe, V, Mo, Ta, Nb, Cr, Mn, Co, Ni, and Cu can be measured by IPC emission spectroscopy. About O and N, using an oxygen-nitrogen simultaneous analyzer, inert gas melting, thermal conductivity, and infrared absorption method can measure. About C, it can measure by infrared absorption method using a carbon-sulfur simultaneous analyzer. About H, it can measure by inert gas melting and an infrared absorption method.

(1.2 metal structure)

Next, the metal structure of the titanium alloy plate which concerns on this embodiment is demonstrated.

The titanium alloy plate according to the present embodiment has an average grain size of 40 µm or less, a standard deviation of the grain size distribution based on the logarithm of the grain size (µm) is 0.80 or less, and the α phase having a hexagonal closest packed structure The area ratio of the crystal grains in which the angle formed by the [0001] direction of the α phase with respect to the plate thickness direction is 0° or more and 40° or less is 70% or more.

Hereinafter, the metal structure of the titanium alloy plate which concerns on this embodiment is demonstrated in detail in order.

(1. 2. 1 phase composition of metal structure)

The metal structure of the titanium alloy plate according to the present embodiment includes an α phase having a hexagonal closest packing structure. The metal structure of the titanium alloy plate according to the present embodiment may contain a β phase in addition to the α phase. However, the β phase is preferentially corroded over the α phase. For this reason, when a titanium drum having a titanium alloy plate containing a β phase on its surface is used for the production of copper foil, the β phase preferentially corrodes and a macro pattern is formed on the drum surface, and the macro pattern is transferred to the copper foil. There is this. In addition, when the β phase is formed by aggregation, there is a possibility that the texture of the titanium alloy plate changes. Therefore, the one with few beta phases is better.

The volume fraction of the α phase in the titanium alloy plate according to the present embodiment is preferably 98.0% or more, more preferably 99.0% or more, and still more preferably 100% (α-phase single phase).

Moreover, it is preferable that a non-recrystallization part is not contained in the metal structure of a titanium alloy plate. These non-recrystallized portions are generally coarse and may cause macro-shape. Therefore, the metal structure of the titanium alloy plate is preferably a completely recrystallized structure. The recrystallized structure is a structure containing crystal grains having an aspect ratio of less than 2.0. The presence or absence of non-recrystallized grains can be confirmed with the following method. That is, crystal grains having an aspect ratio of 2.0 or more are referred to as non-recrystallized grains, and the presence or absence thereof is checked. Specifically, the cross section obtained by cutting the titanium alloy plate is chemically polished, and the electron beam backscattering diffraction method; Using EBSD (Electron Back Scattering Diffraction Pattern), a 1-2 mm x 1-2 mm area|region is a 1-2 micrometer step, and about 2-10 fields of view are measured. After that, the boundary of the orientation difference of 5° or more measured by EBSD is taken as the grain boundary, the range surrounded by the grain boundary is taken as the crystal grain, the long axis and the short axis of the grain are found, and the long axis is divided by the short axis (long axis/short axis) is calculated as the aspect ratio. The major axis means that the length is the largest among the line segments joining two arbitrary points on the grain boundary of the α phase, and the minor axis means that the length is the largest among the line segments orthogonal to the major axis and joining two arbitrary points on the grain boundary. say to be

The metal structure of the α-phase single phase as described above can be achieved by the chemical composition of the titanium alloy plate as described above.

The volume fraction of each phase constituting the metal structure of the titanium alloy plate can be easily measured and calculated by using an Electron Probe Microanalyzer (EPMA) (SEM/EPMA) attached to SEM (Scanning Electron Microscopy). Specifically, an arbitrary cross section of the plate is polished to a mirror surface, and at a magnification of 100 times, a 1 mm x 1 mm area at a position of 1/4 of the plate thickness from the surface in a step of 1 to 2 µm The concentration distribution of Fe or other β-phase stabilizing elements is measured using SEM/EPMA at 2 to 5 field of view. A point (concentrated portion) at which the concentration of Fe or the total concentration of the β-phase stabilizing elements is higher than the average concentration of the measurement range by 1 mass% or more is defined as the β-phase, and the area ratio is obtained. The area ratio and the volume ratio are made equal, and the obtained area ratio is the volume ratio of the β phase, and the area ratio of the portion (other than the thickening portion) in which the β-phase stabilizing element is not concentrated is the volume ratio of the α phase.

(Average particle size and particle size distribution of 1. 2. 2 grains)

Next, the average particle diameter and particle size distribution of the crystal grains contained in the metal structure of the titanium alloy plate which concerns on this embodiment are demonstrated.

First, when the grain size (crystal grain size) of the crystal grains of the metal structure of the titanium alloy plate is coarse, the grain itself becomes a pattern, and since the pattern is transferred to the copper foil, the fine grain size is better. When the average crystal grain diameter of the crystal grains of the metal structure of a titanium alloy plate exceeds 40 micrometers, the crystal grain itself will become a pattern, and a pattern will be transcribe|transferred by copper foil. For this reason, the average grain size of the crystal grains of the metal structure of a titanium alloy plate shall be 40 micrometers or less. Thereby, crystal grains become sufficiently fine, and generation|occurrence|production of a macro pattern is suppressed. The average crystal grain size of the crystal grains of the metal structure of the titanium alloy plate is preferably 38 µm or less, and more preferably 35 µm or less.

In addition, the lower limit of the average grain size of the crystal grain of the metal structure of a titanium alloy plate is not specifically limited. However, when the crystal grains are very small, there is a fear that non-recrystallized portions are generated during heat treatment. For this reason, the average crystal grain size of crystal grains becomes like this. Preferably it is 3 micrometers or more, More preferably, it is 5 micrometers or more, More preferably, it is 10 micrometers or more.

Moreover, in a metal structure, when a beta phase exists, it is preferable that the average crystal grain diameter of a beta phase is 0.5 micrometer or less. When the particle size of the beta phase is large, there is a possibility that large irregularities are formed in the titanium alloy plate by corrosion or polishing. When the average grain size of the β phase is 0.5 µm or less, the formation of irregularities due to corrosion or polishing can be suppressed.

Moreover, the present inventors discovered that a macropattern could not fully be suppressed only when the crystal grain of the metal structure of a titanium alloy plate is only fine. That is, even if the crystal grains of the metal structure of a titanium alloy plate are fine, when a particle size distribution is wide, coarse crystal grains will exist. When there is a region where such coarse grains and fine grains are mixed, a macro shape may occur due to a difference in particle size. For this reason, the present inventors discovered that the crystal grain of the metal structure of a titanium alloy plate is not only fine, but that it is important for suppression of the generation|occurrence|production of a macro pattern that a particle size distribution is narrow, ie, that the grain size of a crystal grain is uniform.

Specifically, in the titanium alloy sheet according to the present embodiment, the standard deviation of the particle size distribution based on the logarithm of each crystal grain size (µm) is 0.80 or less. When the crystal grains satisfy the standard deviation of such a particle size distribution together with the average particle diameter as described above, the crystal grains in the metal structure are sufficiently fine and uniform. As a result, when the titanium alloy plate is used for the drum, the occurrence of macro patterns is suppressed.

On the other hand, if the standard deviation of the grain size distribution based on the logarithm of the grain size (μm) exceeds 0.80, coarse grains are generated even when the average grain size as described above is satisfied, and the titanium alloy plate When used on drums, macro patterns are likely to occur.

It is preferable that the standard deviation of the particle size distribution based on the logarithm of the crystal grain size (µm) is equal to or less than the threshold value (0.35 × InD -0.42) when the average grain size is D (µm).

The average crystal grain size of the crystals of the metal structure of the titanium alloy plate and the standard deviation of the grain size distribution can be measured and calculated as follows. Specifically, the cross section obtained by cutting the titanium alloy plate is chemically polished, and the electron beam backscattering diffraction method; Using EBSD (Electron Back Scattering Diffraction Pattern), a 1-2 mm x 1-2 mm area|region is measured about 2-10 visual fields in a 1-2 micrometer step. Regarding the crystal grain size, the boundary of the orientation difference of 5° or more measured by EBSD is the grain boundary, and the range surrounded by the grain boundary is referred to as the crystal grain, and the equivalent circle size from the area of the grain (area A = π × (grain diameter D/2)) ² ) is calculated|required, and let the average value of this number standard be an average grain size. Moreover, the standard deviation (sigma) in a lognormal distribution can be computed from a crystal grain size distribution. At that time, the distribution standard deviation σ of the converted value obtained by converting the equivalent circle particle diameter D of each crystal grain into the natural logarithm lnD is calculated.

Generally, it is known that the crystal grain size distribution of a metal material follows a lognormal distribution. Therefore, in the calculation of the standard deviation of the particle size distribution as described above, the obtained particle size distribution may be normalized to a lognormal distribution, and the standard deviation may be calculated from the normalized lognormal distribution.

(1. 2. 3 collective organization)

<The area ratio of crystal grains with an angle of 0° or more and 40° or less between the [0001] direction of the α phase with respect to the plate thickness direction is 70% or more>

The crystal structure of the α phase of titanium takes a hexagonal close-packed (hcp) structure. Titanium having an hcp structure has high anisotropy in physical properties due to crystal orientation. Specifically, in titanium of the hcp structure, strength is high in a direction parallel to the [0001] direction (hereinafter also referred to as c-axis direction), and strength is low as it approaches in a direction perpendicular to the c-axis direction. For this reason, even if the titanium alloy plate satisfies the particle size distribution of the crystal grains as described above, for example, when aggregates of crystals having different crystal orientations occur, workability between the aggregates is different, so at the time of copper foil production drum production , the workability at the time of grinding may become different. In this case, in the drum obtained, there exists a possibility that it may be recognized as a macro pattern in the size close|similar to a crystal grain. Therefore, it is preferable to suppress generation|occurrence|production of a macro pattern by integrating the crystal orientation of the texture of a titanium alloy plate as much as possible.

In addition, titanium of the hcp structure has high strength in a direction parallel to the c-axis direction. Therefore, when a surface perpendicular to the c-axis is polished, the shape after polishing is difficult to occur. From this point of view, with respect to the crystal orientation of the texture of the titanium alloy plate, so that it is perpendicular to the polishing surface, that is, in parallel with the thickness direction (normal direction of the plate surface: ND) perpendicular to the surface of the titanium alloy plate, the titanium alloy plate It is preferable to arrange the c-axis of the crystal lattice of

In the titanium alloy plate according to the present embodiment, the area ratio of crystal grains in which the angle θ between the normal direction (ND) of the plate surface and the c-axis ([0001] direction) of the α phase is 40° or less is 70% with respect to the area of all crystal grains More than that. The angle θ is an angle shown in FIG. 4 .

When the area ratio of crystal grains in which the angle θ between the ND and the c-axis of the α phase is 40° or less is 70% or more, the crystal orientations are integrated, and the difference in the crystal orientations between adjacent crystals can be reduced. As a result, the macro shape can be suppressed. The area ratio of crystal grains having an angle θ of 40 degrees or less is preferably 72% or more with respect to the area ratio of all crystal grains. The higher the area ratio, the better. Therefore, in particular, although the upper limit of the area ratio is not set, it is up to about 95% of what can be manufactured substantially.

The angle θ formed by the c-axis of the α phase with respect to the plate thickness direction can be calculated using a (0001) pole figure from the normal direction ND of the plate surface. (0001) The pole figure is obtained by chemically polishing the observation surface of the sample of a titanium alloy plate, and carrying out crystal orientation analysis using EBSD. Specifically, for example, a crystal orientation map as shown in Fig. 5 is obtained by scanning an area of 1 to 2 mm x 1 to 2 mm at intervals of 1 to 2 µm using EBSD.

For example, in the region G1 shown in white in Fig. 5, the angle θ formed between the ND and the c-axis of the α phase is 40° or less, and the region G2 shown in black has the angle θ formed with the c-axis of the α phase. The region G3, which shows crystal grains of more than 40° and less than 60°, and shown in gray, shows crystal grains in which the angle θ formed with the c-axis of the α phase is greater than 60° and less than or equal to 90°. Then, a (0001) pole figure can be drawn by crystal orientation analysis. As shown in FIG. 6 , in the (0001) pole figure, the region R1 surrounded by the dotted line b1 is a region where the angle θ between the plate thickness direction (ND) and the c-axis of the crystal grain is 40° or less, and the dotted line b1 and The region R2 surrounded by the dotted line b2 is a region where the angle θ is greater than 40° and less than 60°, and the region outside the dotted line b2 is a region where the angle θ is 60° or more and 90° or less.

The area ratio of the crystal grains in which the angle (theta) formed between the plate thickness direction (ND) of a titanium alloy plate and the c-axis of an alpha phase is 40 degrees or less is computable as follows. The cross section which cut|disconnected the titanium alloy plate is chemically polished, and crystal orientation analysis is performed using EBSD. For each of the lower surface of the titanium alloy plate and the central portion of the thickness, an area of 1 to 2 mm × 1 to 2 mm is measured in a step of 1 to 2 µm, and about 2 to 10 fields of view are measured. For the data, using OIM Analysis software made by TSL Solutions, the measurement point data where the angle between the ND and the c-axis is 40° or less is extracted. By the above, the angle θ between the thickness direction ND of the titanium alloy plate and the c-axis of the α phase is 40° or less, and the area ratio of the crystal grains is calculated.

<In the (0001) pole figure from the normal direction of the plate surface, by texture analysis of the pole figure using the spherical harmonic function method of electron beam backscattering diffraction (EBSD) method (exponent expansion = 16, Gaussian half width = 5°) The peak of the calculated density exists within 30° from the normal direction of the plate surface, and the maximum density of the (0001) plane has a texture of 4.0 or more>

In the titanium alloy plate according to the present embodiment, in the (0001) pole figure from the normal direction (ND) of the plate surface (rolled surface if it is a rolled material), the peak of the density of crystal grains is 30° from the normal direction (TD) of the plate surface. It is desirable to have a texture, which is present within, and has a maximum degree of integration of 4.0 or higher. Thereby, the c-axis of the crystal grains can be sufficiently integrated in a portion close to the thickness direction (ND) of the titanium alloy plate, and when the titanium alloy plate is used in a copper foil manufacturing drum, the occurrence of patterns due to the difference in crystal orientation is reduced. more restrained

According to rolling or the like, the peak of the degree of integration of crystal grains tends to incline in a direction perpendicular to the final rolling direction (final rolling width direction TD). Therefore, when the final rolling direction is clear, in the (0001) pole figure from the normal direction (ND) of the plate surface, the peak of the density of crystal grains is from the normal direction (ND) of the plate surface to the final rolling width direction (TD) should be within 30°.

(0001) The pole figure is obtained by chemically polishing the observation surface of the sample of a titanium alloy plate, and carrying out crystal orientation analysis using EBSD. For example, as described above, an area of 1 to 2 mm × 1 to 2 mm can be scanned at intervals (steps) of 1 to 2 μm, and a (0001) pole figure can be constructed. At this time, the position with the highest contour line is the peak position of the degree of integration, and the value with the highest degree of integration among the peak positions is set as the maximum degree of integration.

In FIG. 1, an example of the (0001) pole figure from the normal line direction ND in the rolling surface of the titanium alloy plate which concerns on this embodiment is shown. In FIG. 1, the detected pole points are integrated according to the inclination to the last rolling direction RD and the last rolling width direction TD, and the contour line of the integration degree is drawn in the (0001) pole figure. And in FIG. 1, the site|part with the highest contour line becomes the peaks P1 and P2 of the degree of integration of crystal grains. Therefore, in this embodiment, the peaks P1 and P2 of a crystal grain exist within 30 degrees from ND (center), respectively. For example, in the case of the peak P1, a in the figure is within 30° (as in P1 in FIG. 1, the peak position may slightly shift from the TD direction, but a shift within 10° is allowed, and a is within 30° ramen noodles). In addition, the maximum degree of integration is 4.0 or more. Usually, the maximum degree of integration is the degree of integration of the peak P1 or P2 of the crystal grains.

On the other hand, in the (0001) pole figure, when the peak of the degree of integration of crystal grains does not exist within 30° with respect to the final rolling width direction (TD), crystal grains with different crystal orientations are more likely to be adjacent to each other, so that the visible macro shape is more likely to occur Specifically, for example, in a titanium hot-rolled sheet of normal uniaxial rolling, the degree of integration peaks at a portion where the c-axis of the hcp structure is inclined by about 35 to 40° in the final rolling width direction (TD) with respect to the normal ND. A collective organization that becomes However, when the peak is at this position, since the crystal orientation is distributed up to a position further inclined by 15 to 20 degrees, crystal grains having different crystal orientations may be adjacent to each other, and macro-patterns are likely to occur.

A preferable maximum degree of integration is 4.0 or more. Thereby, crystal orientations are sufficiently integrated, and the difference in crystal orientations between adjacent crystals can be reduced. Although the maximum degree of integration is preferably 4.0 or more, for the purpose of further suppressing the occurrence of macro patterns, it is more preferably 5.0 or more, and still more preferably 6.0 or more.

The maximum degree of integration is preferably larger, and therefore the upper limit is not limited, but for example, when controlling the crystal orientation by hot rolling, the upper limit may be about 15 to 20.

The degree of integration of a specific orientation in the (0001) pole figure indicates how many times the frequency of existence of crystal grains having that orientation is for a structure having a completely random orientation distribution (integration figure 1). This degree of integration can be calculated using the texture analysis of the pole figure using the spherical harmonic function method of the electron beam backscattering diffraction (EBSD) method (expanding index = 16, Gaussian half width = 5 degrees). Specifically, the cross section cut out of the titanium alloy plate is chemically polished, and an area of 1 to 2 mm × 1 to 2 mm is measured in a step of 1 to 2 µm for about 2 to 10 fields of view by the EBSD method. The data are calculated by texture analysis of the pole figure using the spherical harmonic function method using OIM Analysis software manufactured by TSL Solutions.

(1. 2. 4 twins)

In titanium, twin deformation may occur during plastic deformation. Twin crystal deformation depends not only on the chemical composition but also on the grain size, and the larger the grain size, the more likely it is to occur. Therefore, the appearance of a crystal grain distribution may become uniform when twin crystals arise.

On the other hand, when twin strain occurs, the crystal orientation difference becomes large, and crystal grains with greatly different crystal orientations are adjacent to each other, and the abrasiveness changes at the boundary, and it is recognized as a pattern. Therefore, it is preferable to suppress twins as much as possible.

Specifically, in the titanium alloy plate according to the present embodiment, when the cross section in the plate thickness direction is observed, the ratio of the twin grain boundary length to the total grain boundary length of the plate thickness cross section at the position of 1/4 plate thickness from the surface It is preferable that this is 5.0% or less. Thereby, the macro pattern resulting from the twin crystal can be reduced to an unrecognizable level. The ratio of the twin grain boundary length with respect to the total grain boundary length becomes like this. More preferably, it is 3.0 % or less, More preferably, it is 1.0 % or less. Although the lower limit of the said ratio may be 0 %, since twin crystal|transformation unavoidably arises by processing, such as correction of a titanium alloy plate, it is difficult to exclude twin crystal completely. In order to reduce twin crystals, it is important to reduce the correction amount, and for example, it is effective to flatten the plate shape of the finish as much as possible.

Calculation of the said ratio WHEREIN: The total grain boundary length and twin grain boundary length of a plate|board thickness cross section can be calculated|required as follows. First, the observation cross section (thickness direction cross section) of the sample of a titanium alloy plate is chemically polished, and crystal orientation is analyzed using the electron beam backscattering diffraction method. An area of 1 to 2 mm × 1 to 2 mm at a position of 1/4 of the plate thickness from the surface of the titanium alloy plate of the sample was scanned at intervals of 1 to 2 μm, using OIM Analysis software manufactured by TSL Solutions. Create an inverse pole figure (IPF) map. At that time, (10-12) twins, (10-11) twins, (11-21) twins, and (11-22) twins generated in titanium must be within 2° from the theoretical value of the rotation axis and crystal orientation difference (rotation angle). It is regarded as a twin interface (for example, in the case of (10-12) twins, the theoretical values of the rotation axis and crystal orientation difference (rotation angle) are <11-20> and 85°, respectively). Then, a grain boundary having a crystal orientation difference (rotation angle) of 2° or more is taken as the total grain boundary length, and the ratio of the twin grain boundary length to the total grain boundary length is calculated. The reason for observing the twin grain boundary at the position of 1/4 of the plate thickness from the surface is that the position can sufficiently represent the structure of the titanium alloy plate. Moreover, it is because the surface of a titanium alloy plate may not fully represent a structure|tissue by grinding|polishing etc.

(1.3 surface hardness)

Although the surface hardness (Vickers hardness) of the surface used as the drum surface of a titanium alloy plate is not specifically limited, It is preferable that it is HV110 or more. Thereby, when a drum is manufactured using a titanium alloy plate and the surface is grind|polished, uniform grinding|polishing becomes possible, and a macro pattern can be suppressed further. The surface hardness (Vickers hardness) of a titanium alloy plate becomes like this. More preferably, it is HV112 or more, More preferably, it is HV115 or more.

In addition, the upper limit of the surface hardness (Vickers hardness) of the surface that becomes the drum surface of the titanium alloy plate is not particularly limited, but if the surface hardness is more than HV350, the number of times of polishing increases and time is required, The productivity of the drum is reduced. Therefore, it is preferable that it is 350 HV or less. More preferably, it is 300 HV or less, More preferably, it is 250 HV or less. Moreover, when making the amount of processing required at the time of correction of a titanium alloy plate sufficiently small, it is preferable that it is HV160 or less. More preferably, it is HV155 or less, More preferably, it is HV150 or less.

The surface hardness of the titanium alloy plate is measured at 3 to 5 points under a load of 1 kg using a Vickers hardness tester in accordance with JIS Z 2244:2009 after the surface of the titanium alloy plate is polished until it becomes a mirror surface, and the average value thereof can

(1.4 thickness)

The thickness of the titanium alloy plate according to the present embodiment is not particularly limited, and can be appropriately set according to the use, specifications, and the like of the drum to be manufactured. When used as a material of a copper foil manufacturing drum, since plate|board thickness reduces with use of a copper foil manufacturing drum, it is preferable that the thickness of a titanium alloy plate shall be 4.0 mm or more, and it is good also as 6.0 mm or more. Although the upper limit of the thickness of a titanium alloy plate is not specifically limited, For example, it is 15.0 mm.

In the present embodiment described above, the chemical composition of the titanium alloy sheet is a chemical composition that suppresses grain growth and reduces strain after hot rolling, and makes crystals not only fine but also uniform within a predetermined standard deviation. In addition, the area ratio of the crystal grains including the α phase whose crystal structure is the hexagonal closest packed structure and the angle formed by the [0001] direction of the α phase with respect to the plate thickness direction is 0° or more and 40° or less is 70% or more are doing Therefore, when it uses for the drum for copper foil manufacture, generation|occurrence|production of a macro pattern can fully be suppressed.

Moreover, when the titanium alloy plate which concerns on this embodiment contains more than 1.8 % and 7.0 % or less of Al, the Young's modulus of a titanium alloy plate improves. As a result, copper foil manufacturing drum manufacture WHEREIN: The shrink fit property of the titanium alloy plate to the surface of a core material improves, and productivity of a copper foil manufacturing drum improves.

As an example in FIG. 2, the photograph of the macro shape of the surface of a titanium alloy plate is shown. The "macro shape" refers to the occurrence of portions of different colors in the form of stripes with a length of several millimeters parallel to the rolling direction as shown in FIG. 2 (for reference, the position of the macro shape in FIG. 3 and FIG. 2 ) The drawing is shown with the macro shape highlighted so that you can see it). When such a pattern generate|occur|produces abundantly, a pattern will be transcribe|transferred to the copper foil finally manufactured.

About macro patterns, although it occurs in the manufacturing process of copper foil, for the tendency to produce macro patterns in a titanium alloy plate (the rate of occurrence of macro patterns under the same conditions), the surface of the titanium alloy plate was sanded with #800 sandpaper. It can evaluate by grinding|polishing by using a nitric acid 10%, hydrofluoric acid 5% solution, corroding the surface, and observing.

<Copper foil manufacturing drum>

As explained above, when the titanium alloy plate which concerns on this embodiment uses for the drum for copper foil manufacture, generation|occurrence|production of a macro pattern can fully be suppressed, and it is suitable as a material of a copper foil manufacturing drum.

With reference to FIG. 8, the copper foil manufacturing drum 20 which concerns on this embodiment is a part of an electrodeposition drum, The cylindrical inner drum 21 and the titanium alloy plate adhered to the outer peripheral surface of the said inner drum 21. (22) and the welding part 23 provided in the butt|matching part of the said titanium alloy plate 22, The said titanium alloy plate 22 is the titanium alloy plate which concerns on this embodiment mentioned above.

That is, the copper foil manufacturing drum 20 which concerns on this embodiment is a copper foil manufacturing drum manufactured using the titanium alloy plate which concerns on this embodiment. Since the copper foil manufacturing drum 20 which concerns on this embodiment uses the titanium alloy plate which concerns on this embodiment for the surface of the drum on which copper foil deposits, generation|occurrence|production of a macro pattern is suppressed, and high-quality copper foil is manufactured can do.

Although the size in particular of the copper foil manufacturing drum which concerns on this embodiment is not restrict|limited, The diameter of a drum is 1-5 m, for example.

The inner drum 21 may be a well-known thing, and the raw material may not be a titanium alloy plate, for example, mild steel or stainless steel may be sufficient as it.

The titanium alloy plate 22 is wound on the outer peripheral surface of the cylindrical inner drum 21 and adhered to the inner drum by welding the butt portion. Therefore, the welding part 23 exists in the butt|matching part.

In the welded part of the copper foil manufacturing drum which concerns on this embodiment, a metal structure is a volume ratio, has 98.0% or more of alpha phases, is a particle size number based on JIS G 0551:2013, and is 6 or more and 11 or less. The particle size number is preferably 7 or more and 10 or less.

When the grain diameter (crystal grain size) of the crystal grain of the metal structure of a welding part is coarse, the crystal grain itself will become a pattern, and a pattern will be transcribe|transferred to copper foil. When the crystal grains are so fine in the metal structure of the welded portion, the generation of patterns due to the crystal grains is suppressed.

According to JIS G 0551:2013, the grain size number of the crystal grain of the metal structure of a weld part can be measured by the comparative method, the counting method, and the cutting method.

The welding part 23 of the copper foil manufacturing drum 20 which concerns on this embodiment has the following metal structures, for example.

The metal structure of the weld zone is mainly α-phase, that is, mainly includes α-phase. The β phase is preferentially corroded over the α phase. For this reason, from a viewpoint of achieving uniform corrosion and suppressing generation|occurrence|production of a macro pattern, it is preferable that there are few β-phases. On the other hand, when the β phase is present in a small amount, crystal grain growth during heat treatment can be suppressed, so that a uniform and fine grain size can be obtained. From such a viewpoint, it is preferable that the volume ratio of the β-phase in the metal structure of the weld zone is 2.0% or less. In this case, the remainder of the metal structure of the titanium alloy plate is the α phase. The volume fraction of the β phase is preferably 1.0% or less, and more preferably, the texture of the weld zone is an α single phase. Moreover, the volume ratio of the alpha phase in the metal structure of the welding part which concerns on this embodiment becomes like this. Preferably it is 98.0 % or more, More preferably, it is 99.0 % or more, More preferably, it is 100 %.

The volume fraction of each phase constituting the metal structure of the welded portion can be obtained by the same method as that of the base material portion.

In addition, when the difference in hardness between the welded portion and the drum base material is large, there may be a case where a level difference occurs during polishing. Therefore, it is preferable that the difference in hardness (Vickers hardness) of a weld part and a drum base material is ±25 or less. More preferably, it is ±15 or less. Thereby, when a drum is manufactured using a titanium alloy plate and the surface is grind|polished, uniform grinding|polishing becomes possible, and a macro pattern can be suppressed further. The hardness of the weld zone is, for example, HV110 or more, more preferably HV112 or more, still more preferably HV115 or more.

The hardness of the weld zone can be measured at 3 to 5 points under a load of 1 kg using a Vickers hardness tester according to JIS Z 2244:2009, after polishing the weld zone surface to a mirror surface, and the average value thereof.

Moreover, it is preferable that the difference (difference of a grain size number) of the crystal grain size of the welding part to be formed and the crystal grain size of a titanium alloy plate is -1.0 or more and 1.0 or less. By reducing the difference in grain size between the welded portion and the other portions, the occurrence of macro patterns is more reliably suppressed.

<2. The manufacturing method of the titanium alloy plate which concerns on this embodiment>

Although the titanium alloy plate which concerns on this embodiment demonstrated above may be manufactured by any method, for example, it can manufacture with the manufacturing method of the titanium alloy plate which concerns on this embodiment demonstrated below.

A preferable manufacturing method of the titanium alloy plate according to the present embodiment is

(I) a first step (heating step) of heating a titanium alloy having the above-described chemical composition at a temperature of 750° C. or higher and 950° C. or lower;

(II) a second step (rolling step) of rolling after the heating step to obtain a titanium alloy plate;

(III) Third step of annealing the titanium alloy after the rolling step (annealing step)

has Hereinafter, each process is demonstrated.

(2.1 Preparation of material of titanium alloy plate)

First, prior to each process described above, the material of the titanium alloy plate is prepared. As a raw material, the thing of the above-mentioned chemical composition can be used, and the thing manufactured by a well-known method can be used. For example, an ingot is produced from sponge titanium by various melting methods such as a vacuum arc remelting method, an electron beam melting method, or a furnace melting method such as a plasma melting method. Next, a raw material can be obtained by hot forging or rolling the obtained ingot at the temperature of the α-phase high-temperature region or the β-phase single-phase region. The raw material may be subjected to a pretreatment such as a washing treatment or cutting, if necessary. In addition, when the rectangular slab shape which can be hot rolled is manufactured by the hearth melting method, you may provide directly to the following 1st process and 2nd process (heating, hot rolling) without performing hot forging etc.

(2. 2 first step)

This step is a heating step performed prior to hot rolling of the titanium material. In this process, the raw material of a titanium alloy plate is heated at the temperature of 750 degreeC or more and 950 degrees C or less. When heating temperature is 750 degreeC or more, it can prevent that the crack of a titanium alloy plate generate|occur|produces in the hot rolling of a 2nd process. In addition, when the heating temperature is 950° C. or higher, it is possible to prevent the generation of a texture (T-texture) in which the c-axis of the hcp structure is oriented in the sheet width direction in the hot rolling of the second step.

On the other hand, if the heating temperature is less than 750 ° C., for example, when coarse particles are generated in hot forging, casting, etc., in the hot rolling in the second step, cracks are generated in the titanium alloy plate with the coarse particles as the starting point. may be thrown away.

In addition, when the heating temperature exceeds 950°C, a coarse texture (T-texture) in which the c-axis of the hcp structure is oriented in the sheet width direction in the hot rolling of the second step is generated. In this case, the structure in which the area ratio of the crystal grains in which the angle formed by the [0001] direction of the α phase with respect to the plate thickness direction as described above is 0° or more and 40° or less is 70% or more is not obtained. When the heating temperature is 950°C or less, the generation of T-texture can be prevented. Therefore, the heating temperature is 950°C or less. The heating temperature is preferably below the β transformation point, more preferably at most 900°C or below (β transformation point -10°C).

In addition, in the (0001) pole viscosity from the normal direction of the plate surface, the peak of the density of crystal grains exists within 30° with respect to the final rolling width direction, and in order to obtain a texture having a maximum density of 4.0 or more, the heating temperature is 900 It is preferable that it is below [degrees]C, and especially when Al content is 3.0 % or less, as for heating temperature, 880 degreeC or less is preferable.

In the present embodiment, the "β transformation point" means the boundary temperature at which the α phase starts to form when the titanium alloy is cooled from the β phase single-phase region. The β transformation point can be obtained from the state diagram. A phase diagram can be acquired by the CALPHAD(Computer Coupling of Phase Diagrams and Thermochemistry) method, for example. Specifically, the phase diagram of the titanium alloy can be obtained by the CALPHAD method using Thermo-Calc, an integrated thermodynamic calculation system of Thermo-Calc Software AB, and a predetermined database (TI3), and the β transformation point can be calculated.

(2.3 second process)

In this process, the raw material of the heated titanium alloy plate is rolled (hot rolling). In this step, the total reduction ratio is set to 80% or more, and the ratio of the rolling reduction ratio of the rolling at 200°C or more to 650°C or less among the total reduction ratios is 5% or more and 70% or less. It is preferable to do Thereby, a texture in which the crystal grains are uniformly refined as described above and the c-axis of the hcp structure is highly integrated along the plate thickness direction is obtained. The hot rolling start temperature in this step is basically the heating temperature.

When the total reduction ratio is 80% or more, coarse particles generated in hot forging, casting, or the like can be sufficiently miniaturized, and T-texture can be prevented from occurring. When the total reduction ratio is less than 80%, the structure generated during hot forging, casting, or the like remains, and coarse grains are formed or T-texture may be generated. When such a structure is generated, a macro pattern is generated in the drum to be manufactured.

The total rolling reduction in this step is preferably 85% or more when the Al content is 3.0% or less. In addition, the higher the reduction ratio, the better the structure. Therefore, it may be determined according to the required product size and the characteristics of the manufacturing mill.

Moreover, in the manufacturing method of the titanium alloy which concerns on this embodiment, the ratio which the rolling reduction ratio of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less occupies among the total reduction ratios is 5% or more and 70% or less. It is preferable to do In particular, when Al content is small (for example, 3.0% or less), it is preferable to satisfy the above.

In the case where the ratio of the rolling reduction ratio of the titanium alloy sheet at 200°C or more to 650°C or less among the total reduction ratios is less than 5%, such as when all rolling is performed at more than 650°C, in this temperature range The amount of rolling reduction is not sufficient, and recovery occurs during subsequent cooling, and a portion with a small amount of deformation occurs. Therefore, the fluctuation|variation of a crystal grain size becomes large by the heat processing after hot rolling. Variations in the grain size are particularly likely to occur when the Al content, which suppresses grain growth, is small.

Moreover, by making the ratio which the rolling reduction ratio of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less account for 5 % or more and 70 % or less, a crystal structure contains the alpha phase which is a hexagonal closest packing structure, and plate|board thickness direction The peak of the density of crystal grains in the (0001) pole figure from the normal direction of the tissue and/or plate surface with an area ratio of crystal grains with an angle of 0° or more and 40° or less to 70% or more is the final It exists within 30 degrees with respect to the rolling width direction, and it becomes easy to obtain the texture whose maximum integration degree is 4.0 or more.

On the other hand, in the case where voltage rolling is performed at less than 200 degreeC, when the ratio which the rolling reduction ratio of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less occupies among the total rolling reduction ratios is less than 5 %, a plate shape becomes unstable. In this case, the amount of processing in the subsequent straightening becomes large, the strain is introduced, the difference in the amount of strain between the straightening part and the other parts becomes large, and the fluctuation of the crystal grain size becomes large in the subsequent heat treatment. Further, if further correction is performed after heat treatment, deformation is affected, and only that portion is liable to be corroded, which may cause macro-patterning. The ratio for the rolling reduction of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less among the total reduction ratios becomes like this. Preferably it is 10 % or more, More preferably, it is 15 % or more.

On the other hand, when the ratio of the rolling reduction ratio of the titanium alloy sheet in 200°C or more to 650°C or less among the total reduction ratios exceeds 70%, the plate shape becomes unstable, such as when voltage rolling is performed at 650°C or less. . In this case, the amount of processing in the subsequent straightening becomes large, the strain is introduced, the difference in the amount of strain between the straightening part and the other parts becomes large, and the fluctuation of the crystal grain size becomes large in the subsequent heat treatment. Further, if further correction is performed after heat treatment, deformation is affected, and only that portion is likely to be corroded, which may cause macro-patterning.

Therefore, as for the ratio which the rolling reduction ratio of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less occupies among the total reduction ratios, 70 % or less is preferable. More preferably, it is 65 % or less, More preferably, it is 60 % or less.

It is preferable that the surface temperature of the titanium alloy plate at the time of the completion of hot rolling in this process is 200 degreeC or more. By making the surface temperature of the titanium alloy plate at the time of completion of hot rolling into 200 degreeC or more, it can suppress that the shape of a titanium alloy plate becomes unstable, and the processing amount by subsequent correction can be reduced. Thereby, the amount of deformation introduced into the titanium alloy plate is reduced, and variations in the grain size that may occur in subsequent heat treatment are reduced. In addition, when deformation is introduced, only that portion is likely to be corroded, which may cause macro-shape, but by setting the surface temperature of the titanium alloy sheet at the completion of hot rolling to 200° C. or higher, the amount of processing at the time of correction can be reduced. It is possible to reduce the amount of deformation introduced into the titanium alloy plate, it is possible to suppress the macro shape. The surface temperature of the titanium alloy plate at the time of completion of hot rolling becomes like this. Preferably it is 300 degreeC or more.

In addition, in this process, although the unidirectional rolling extended|stretched in the longitudinal direction of a titanium alloy plate may be sufficient as rolling, you may perform rolling in the direction orthogonal to the said longitudinal direction other than rolling in a longitudinal direction. Thereby, in the obtained titanium alloy plate, the integration degree of a texture can be raised further.

Specifically, when the reduction ratio by rolling in the final rolling direction is L (%) and the reduction ratio by rolling in the direction orthogonal to the final rolling direction is T (%), L/T is 1.0 or more and 10.0 It is preferable that it is below. Thereby, in the obtained titanium alloy plate, the integration degree of a texture can be raised further. L/T becomes more preferably 1.0 or more and 5.0 or less.

This process WHEREIN: In performing the rolling in 200 degreeC or more and 650 degrees C or less, you may hold|maintain for a fixed time and wait for a titanium alloy plate to cool.

In the manufacturing method of the titanium alloy plate which concerns on this embodiment, it is preferable not to reheat and roll during a 2nd process. Thereby, it is prevented that the deformation|transformation which arises in rolling is relieved by reheating, and a deformation|transformation can be provided to a titanium alloy plate stably. As a result, while being able to raise the integration degree of the texture of a titanium alloy plate, the partial abnormal grain growth at the time of the heat processing mentioned later can be suppressed.

You may perform cold rolling after a 2nd process. Cold rolling is rolling at the temperature of 200 degrees C or less, and may be performed by unidirectional rolling or cross rolling. The reduction ratio is preferably 10% or more. By setting the reduction ratio to 10% or more, it is possible to uniformly introduce strain, and it is possible to reduce variations in grain size that may occur in subsequent heat treatment.

When performing cold rolling, the oxide scale on the surface of the titanium alloy plate after hot rolling is previously removed. Removal of oxide scale may be performed by shot blasting, pickling following shot blasting, for example, and may be performed by machining, such as cutting. Before removal of the oxide scale, if necessary, annealing may be performed at a temperature lower than the β transformation point. Such annealing is preferably performed at (β transformation point -50)°C or lower.

When performing cold rolling, when there is too much Al content of a titanium alloy plate, cold ductility may run short and a titanium alloy plate may crack. Therefore, it is preferable that Al content of the titanium alloy plate in the case of cold rolling is 3.5 % or less.

In addition, when making small the ratio of the twin grain boundary length with respect to the total grain boundary length, it is preferable not to perform cold rolling.

(2.4 third process)

In this process, the titanium alloy plate is heat-processed (annealed) for 20 minutes or more at the temperature of 600 degreeC or more and β transformation point °C or less. Thereby, fine recrystallized grains can be precipitated as fine recrystallized grains, and the crystal|crystallization in the metal structure of the titanium alloy plate obtained can be made into fine grain uniformly. As a result, generation|occurrence|production of a macro pattern can be suppressed more reliably.

Specifically, non-recrystallized grains can be sufficiently precipitated as recrystallized grains by heat-treating the titanium alloy sheet at a temperature of 600°C or higher for 20 minutes or more. Annealing temperature becomes like this. Preferably it is 650 degreeC or more. From a viewpoint of suppressing the coarsening of a crystal grain, it is preferable to make annealing temperature below the beta transformation point. More preferably, it is 800 degrees C or less.

Although the upper limit of annealing time is not specifically limited, For example, it is 5 hours or less. In particular, when there is little Al content which has a crystal grain growth suppression effect, it is preferable to make annealing time into 90 minutes or less from a viewpoint of suppressing coarsening of a crystal grain.

The heat treatment may be performed in an atmospheric atmosphere, an inert atmosphere, or a vacuum atmosphere. However, when oxide scale is formed in a titanium alloy plate, oxide scale is removed. The removal of oxide scale is not restrict|limited in particular, For example, you may perform by shot blasting, pickling following shot blasting, and may perform by machining, such as grinding|polishing and cutting. However, in shot blasting, since there is a possibility that a deformation|transformation may introduce|transduce into a titanium alloy plate, it is better to avoid removal of oxide scale by shot blasting.

In addition, the annealing method in particular is not restrict|limited, A continuous heating system may be sufficient and a batch heating system may be sufficient.

(2.5 post-treatment process)

As a post-process, removal of oxidized scale etc. by pickling or cutting, a washing process, etc. are mentioned, It can apply suitably as needed. Or as a post-process, you may perform correction processing of a titanium alloy plate. The straightening process can be performed, for example by vacuum creep flattening (VCF).

As mentioned above, the manufacturing method of the titanium alloy plate which concerns on this embodiment was demonstrated.

Next, the manufacturing method of the copper foil manufacturing drum which concerns on this embodiment is demonstrated.

The manufacturing method of the copper foil manufacturing drum which concerns on this embodiment is the titanium wire for welding (titanium wire for welding which concerns on this embodiment which concerns on this embodiment which mentions two adjacent ends of the titanium alloy plate which processed into cylindrical shape later) ) using a welding process (welding process).

The processing to the cylindrical shape of a titanium alloy plate, welding conditions, etc. can be made into a well-known method.

At the time of welding, for example, two adjacent ends of the titanium alloy plate processed into a cylindrical shape are brazed using the above-mentioned titanium wire for welding, and a welding part (brazing welding part) is formed. Here, in order to perform cold or warm working with respect to a welded part, it is preferable to perform preliminary brazing on a brazing part. The thickness of the preliminary brazing can be, for example, 10 to 50% of the thickness of the titanium alloy plate.

In addition, about the brazing weld part, you may roll-down in cold or the warm temperature of 200 degrees C or less. Thereby, the solidification structure of a brazing weld part can be made into a uniform fine equiaxed structure. In order to prevent the generation of shavings due to a high working rate and to make the solidified structure into a uniform fine equiaxed structure with certainty, the reduction ratio is preferably 10% or more and 50% or less.

Moreover, you may perform heat processing (annealing) after welding. The heat treatment can be performed, for example, at a temperature of 500°C or more and 850°C or less for 1 minute or more and 10 minutes or less. By performing the heat treatment at 850°C or less for 10 minutes or less, coarsening of the crystal grains or a part of the crystal grains are prevented from being coarsened, and a uniform fine crystal structure can be obtained.

Next, the titanium wire for welding used for manufacture of the copper foil manufacturing drum which concerns on this embodiment is demonstrated.

<Titanium wire rod for welding>

The titanium wire rod for welding according to the present embodiment can be used to manufacture a copper foil-made titanium drum, and more specifically, is used to weld adjacent ends of a titanium alloy plate bent into a cylindrical shape.

The titanium wire for welding according to the present embodiment, by mass%,

At least one selected from the group consisting of Sn, Zr and Al: 0.2% or more and 6.0% or less in total

O: 0.01% or more and 0.70% or less;

N: 0.100% or less;

C: 0.080% or less;

H: 0.015% or less, and

Fe: 0.500% or less,

It is preferable that the balance has a chemical composition containing Ti and impurities.

One or more types of content selected from the group which consists of Sn, Zr, and Al are 0.2 mass % or more and 6.0 mass % or less in total. Thereby, since the metal structure of the weld part obtained can be made into the main α phase, and the production|generation of the β phase can be suppressed, the corrosion resistance of a weld part can be improved. Furthermore, the crystal grains in the metal structure of the weld part obtained can be made fine enough, and generation|occurrence|production of the macro pattern resulting from a crystal grain can be suppressed.

On the other hand, when the content of at least one selected from the group consisting of Sn, Zr, and Al is less than 0.2% by mass in total, coarse particles may be generated in the crystal grains in the metal structure of the welded part obtained, and the occurrence of macro patterns is suppressed Can not. The content of at least one selected from the group consisting of Sn, Zr, and Al is preferably 0.3% by mass or more in total, and more preferably 0.4% by mass or more in total.

In addition, when the content of at least one selected from the group consisting of Sn, Zr and Al exceeds 6.0% by mass in total, macro-shaped in the welded portion obtained by adverse effects caused by excessively containing Sn, Zr and Al described above. occurrence cannot be suppressed. The content of one or more selected from the group consisting of Sn, Zr, and Al is preferably 5.5 mass% or less in total, and more preferably 5.0 mass% or less in total.

Among the elements mentioned above, Sn is a neutral element, and is an element which can suppress the growth of the crystal grain of a welding part by containing it in the titanium wire for welding. In order to suppress the growth of a crystal grain stably, Sn content becomes like this. Preferably it is 0.2 mass % or more, More preferably, it is 0.3 mass % or more.

On the other hand, when Sn is added excessively, depending on the chemical composition, it segregates in the longitudinal direction of the titanium wire for welding, and a macro pattern derived from concentration may be formed in the bead welded portion. For this reason, Sn content becomes like this. Preferably it is 6.0 mass % or less, More preferably, it is 5.5 mass % or less.

Zr is also a neutral element, and is an element capable of suppressing crystal grain growth by containing it in the titanium wire for welding. In order to suppress crystal grain growth stably, Zr content becomes like this. Preferably it is 0.2 mass % or more, More preferably, it is 0.3 mass % or more.

On the other hand, when Zr is added excessively, the α+β region near the transformation temperature is widened depending on the chemical composition, and the β phase tends to precipitate in the heat treatment at the time of manufacturing the titanium drum made of copper foil. Moreover, as a result of which a difference in surface strength arises by solidification segregation, a macro pattern may generate|occur|produce at the time of surface grinding|polishing of the titanium drum made from copper foil. For this reason, Zr content becomes like this. Preferably it is 5.5 mass % or less, More preferably, it is 5.0 mass % or less.

Al is an α stabilizing element, and by containing it in the titanium wire for welding similarly to Sn and Zr, growth of crystal grains can be suppressed, and it contributes to the improvement of the strength of the titanium wire for welding and a weld formed using the same. In order to suppress crystal grain growth stably, Al content becomes like this. Preferably it is 0.2 mass % or more, More preferably, it is 0.3 mass % or more.

On the other hand, if the Al content is excessive, the increase in high-temperature strength becomes large depending on the chemical composition, and the reaction force becomes too large in the processing before heat treatment of the solidified structure (weld portion) of the titanium wire for welding, which may cause processing cracks. The difference between the hardness of the base material and the base material becomes large, and a level difference may occur at the time of polishing and face-up of the titanium drum made of copper foil. For this reason, Al content becomes like this. Preferably it is 5.0 mass % or less, More preferably, it is 4.5 mass % or less.

As mentioned above, Al is an element which can contribute to the improvement of the intensity|strength of a weld part, and raises the hardness of a weld part. For this reason, when suppressing the hardness raise of a welding part, it is preferable to contain it with Sn and/or Zr.

In such a case, for example, content of the sum total of Sn and Al is 0.2 mass % or more and 6.0 mass % or less, Preferably they are 0.3 mass % or more and 5.5 mass % or less. Moreover, for example, content of the sum total of Zr and Al is 0.2 mass % or more and 6.0 mass % or less, Preferably they are 0.3 mass % or more and 5.5 mass % or less.

The above-mentioned Sn, Zr, and Al may be contained in the above-mentioned amounts in total, and any one or two types may not be contained in the titanium wire for welding.

O is an α stabilizing element, and while suppressing an increase in high-temperature strength, the strength at room temperature can be improved, and the hardness of the weld can be improved. In order to acquire this effect, O content shall be 0.01 mass % or more. From a viewpoint of controlling the hardness of a welding part, O content becomes like this. Preferably it is 0.015 mass % or more, More preferably, it is 0.02 mass % or more.

On the other hand, when O content exceeds 0.70 mass %, the crack in brazing will arise at the time of welding. Therefore, O content is 0.70 mass % or less. O content becomes like this. Preferably it is 0.60 mass % or less, More preferably, it is 0.50 mass % or less.

At least a part of O is present in the titanium wire for welding as oxides of Ti, Sn, Zr and/or Al in the form of particles, for example, as TiO ₂ , SnO, SnO ₂ , ZrO ₂ , Al ₂ O ₃ . It is preferable to do These oxides are dissociated by the arc at the time of welding, and the dissociated O forms an oxide film in the welded part, suppresses the arc's local contact, and stabilizes, thereby homogenizing the welded part. Thereby, at the time of welding, a brazing shape and workability|operativity can be improved. O is considered to be uniformly dissolved in the drum weld.

More specifically, the peak intensities of α-titanium obtained by X-ray diffraction with respect to the titanium wire for welding are A, TiO ₂ (110), ZrO ₂ (111), SnO ₂ (110) and Al ₂ O ₃ ( 104), when the sum of the peak intensities is B, it is preferable that B/A (line intensity ratio) is 0.01 or more. Thereby, a sufficient amount of oxide is contained in the titanium wire for welding, and the above-described effect can be sufficiently obtained. B/A becomes like this. More preferably, they are 0.015 or more and 0.10 or less, More preferably, they are 0.02 or more and 0.09 or less.

X-ray diffraction of the titanium wire for welding according to the present embodiment is performed using a Cu tube in a cross section perpendicular to the longitudinal direction at a current of 40 mA, a voltage of 40 kV, and a range of 10 to 110 degrees of 2θ. The measurement can be performed at an interval of 0.01°, 1 s/point, and rotating the sample by 360° at each measurement point.

Fe is an element that strengthens the β phase. In the weld zone, if the amount of β-phase precipitation increases, the formation of macro patterns is affected. Therefore, the upper limit of the Fe content in the titanium wire for welding is set to 0.500%. Fe content becomes like this. Preferably it is 0.100 % or less, More preferably, it is 0.080 % or less.

When all of N, C, and H are contained in a large amount, they are elements that reduce ductility and workability. Therefore, the N content is limited to 0.100% or less, the C content is limited to 0.080% or less, and the H content is limited to 0.015% or less, respectively.

Each of N, C and H is an impurity, and the lower the content thereof, the more preferable. However, these elements may be mixed in the manufacturing process, and the lower limit of the substantial content may be 0.0001% for N, 0.0005% for C, and 0.0005% for H.

The remainder of the chemical composition of the titanium wire for welding according to the present embodiment contains titanium (Ti) and impurities, and may consist of Ti and impurities. Concretely, the impurity is Cl, Na, Mg, Si, Ca mixed in the refining process, and Cu, Mo, Nb, Ta, V, etc. mixed from scrap. When these impurity elements are contained, the content is, for example, 0.10 mass % or less, respectively, and is a level without a problem if it is 0.50 mass % or less in total.

The wire diameter of the titanium wire for welding which concerns on this embodiment is not specifically limited, For example, they are 0.8 mm or more and 3.4 mm or less.

The cross-sectional image of the titanium wire for welding according to the present embodiment is not particularly limited as long as it can be used for welding, and may have any shape.

Manufacture of the titanium wire for welding can be performed by cold, warm, and hot plastic working by hole die drawing, roll die drawing, caliber rolling, etc., or powder metallurgy, for example.

As mentioned above, according to this embodiment, when the titanium wire for welding contains an appropriate amount of at least one selected from the group consisting of Sn, Zr, and Al, it is possible to refine the crystal grains while the structure of the weld zone is mainly α-phase. In addition, by containing O in an appropriate amount in the titanium wire for welding, the hardness of the welding part can be controlled. As a result, in the titanium drum made from copper foil, generation|occurrence|production of the macro pattern resulting from a welding part is suppressed.

In particular, when the titanium wire for welding contains oxides of Ti, Sn, Zr, and/or Al in the form of particles, the method of including in the wire rod by powder metallurgy or attaching the oxide to the surface of the bar and wire drawing to press the oxide on the surface The titanium wire for welding can be manufactured by the method of making the metal wire or by attaching an oxide to the surface of the rod and performing vacuum annealing at 750 to 1000° C. to conduct diffusion bonding. There is also a method of manufacturing a titanium wire for welding by inserting a powdery oxide into a hollow titanium tube, but fluctuations in the distribution of oxides are easy to occur. A change in hardness or crystal grain size occurs. For this reason, in this embodiment, the method of inserting a powdery oxide in a titanium tube is not employ|adopted, and it sets it as the object outside.

Example

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is demonstrated concretely, showing an Example. The examples shown below are merely examples of the present invention, and the present invention is not limited to the following examples.

1. Manufacture of titanium alloy plate

First, an ingot having the chemical composition of Tables 1 and 2 was produced by the vacuum arc remelting method, and by hot forging this, the raw material of the titanium alloy plate of a predetermined composition was obtained.

Next, the obtained titanium alloy plate raw material was heated to the temperature shown in Table 3, Table 4 (1st process), and it hot-rolled on the conditions shown in Table 3, Table 4 (2nd process). "Ratio of the rolling reduction ratio of 200-650 degreeC" in the table means the ratio of the rolling reduction ratio of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less among the total rolling reduction ratios, and "rolling ratio (L/T )" represents the value of L/T when L (%) is the reduction ratio by rolling in the final rolling direction and T (%) is the reduction ratio by rolling in the direction orthogonal to the final rolling direction. . In addition, in each invention example and comparative example shown in Table 1 and Table 2, in order to perform rolling of the titanium alloy plate in 200 degreeC or more and 650 degrees C or less except Comparative Example 1, hot rolling is temporarily stopped, It waited for cooling to 650 degreeC or less, and restarted hot rolling.

In some examples, annealing and cold rolling were performed before cold rolling.

Next, in an atmospheric atmosphere, at the temperature and time described in Tables 3 and 4, heat processing was performed (3rd process), and the 8.0-15.0 mm-thick titanium alloy plate was obtained.

2. Analysis and evaluation

About the titanium alloy plate which concerns on each invention example and a comparative example, it analyzed and evaluated about the following items.

2. 1 grain size

The average crystal grain size D of the crystals of the metal structure of the titanium alloy sheet and the standard deviation of the grain size distribution were measured and calculated as follows. The cross section which cut|disconnected the titanium alloy plate was measured for 10 fields of view in a 2 micrometer step in the area|region of 2 mm x 2 mm using chemical polishing paper and electron beam backscattering diffraction method. Thereafter, regarding the crystal grain size, the equivalent circle grain size (area A = π × (grain size D/2) ² ) is obtained from the grain area measured by EBSD, and the average value of this number basis is referred to as the average grain size D, and The standard deviation σ in the lognormal distribution was calculated from the grain size distribution.

2. 2 collective organization

In the following method, the angle θ between the thickness direction (ND) of the titanium alloy plate and the [0001] direction (c-axis) of the α phase was calculated to be an area ratio of crystal grains of 40° or less.

The cross section cut out of the titanium alloy plate is chemically polished, and crystal orientation analysis is performed using EBSD. About each of the titanium alloy plate surface lower part and the plate|board thickness center part, 10 field-of-view measurements were carried out by step 2 micrometers in the area|region of 2 mm x 2 mm. For the data, measurement point data with an angle between the ND and c-axis of 40° or less was extracted using OIM Analysis software manufactured by TSL Solutions.

(0001) pole figure was obtained by chemically polishing the observation surface of the sample of the titanium material concerning each invention example and comparative example, and performing crystal orientation analysis using the electron beam backscattering diffraction method. More specifically, an area of 2 mm × 2 mm was scanned at an interval of 2 μm, and OIM Analysis software manufactured by TSL Solutions was used, and a (0001) pole figure was plotted. At this time, the position with the highest contour line was set as the peak position of the degree of integration, and the largest value of the degree of integration among the peak positions was set as the maximum degree of integration. The maximum degree of integration was calculated using the texture analysis of the pole figure using the spherical harmonic method (exponent expansion = 16, Gaussian half width = 5°).

2. 3 Al segregation

The presence or absence of Al segregation (Al uniformity) was confirmed as follows. By EPMA, the beam diameter is set to 500 µm and the step size is set to 500 µm equal to the beam diameter, and from the surface of the titanium alloy plate, a plane perpendicular to the plate thickness direction at a position of 1/4 of the plate thickness is 20 mm x 20 A compositional analysis was performed for an area of mm or larger. And in order to convert the composition analysis result into alloy element concentration, JIS Class 1 industrial pure titanium and the target titanium alloy plate were analyzed, and the calibration curve obtained by linear approximation as a result was used. And the area ratio of the area|region whose Al density|concentration is ([Al%]-0.2) mass % or more and [Al%]+0.2) mass % or less was calculated|required.

2. 4 twins

The thickness direction cross section of the sample of the titanium alloy plate which concerns on each invention example and the comparative example was chemically polished, and crystal orientation analysis was carried out using the electron beam backscattering diffraction method. Specifically, a region of 2 mm × 2 mm at a position of 1/4 of the plate thickness from the surface of the titanium alloy plate of the sample is scanned at intervals of 2 µm, and an inverse pole figure (IPF) map is obtained. written. At that time, the twin interface is within 2° from the theoretical value of the rotation axis and the crystal orientation difference (rotation angle) of the (10-12) twin, (10-11) twin, (11-21) twin, and (11-22) twin that occurred. was considered. Then, a grain boundary having a crystal orientation difference (rotation angle) of 2° or more was taken as the total grain boundary length, and the ratio of the twin grain boundary length to the total grain boundary length was calculated.

2. Area ratio of 5 α phase

The thickness direction cross section of the titanium alloy plate according to each invention example and comparative example is mirror polished, and by SEM/EPMA, the concentration of the β-phase stabilizing element in the copper cross section at a position of 1/4 of the plate thickness from the surface. The distribution was measured, and the portion in which the β-phase stabilizing element was not concentrated was calculated as the area ratio of the α-phase.

2. 6 surface hardness

About the surface hardness of the titanium alloy plate which concerns on each invention example and the comparative example, after grinding|polishing the titanium alloy plate surface until it becomes a mirror surface, based on JIS Z 2244:2009, using a Vickers hardness tester with a load of 1 kg 3 to Five points were measured, the obtained value was averaged, and it was set as the surface hardness.

2. 7 macro shapes

For the macro pattern, the surface of the titanium alloy plate according to each invention example and comparative example with a size of about 5 to 10 sheets of 50 × 100 mm was polished with #800 sandpaper, and a 10% nitric acid and 5% hydrofluoric acid solution was used. It was observed by corroding the surface. Next, the pattern of the stripe shape which the length of 3 mm or more generate|occur|produced was made into a macro pattern, and it evaluated as follows according to the average of the generation|occurrence|production ratio.

A: Occurrence rate is 1.0 or less per sheet (Very good, 1.0 or less in 50×100 mm)

B: Occurrence ratio exceeds 1.0/sheet and less than 5.0/sheet (good, more than 1.0 and 5.0 or less in 50×100 mm)

C: Occurrence rate of more than 5.0 pieces/sheet and 10.0 pieces/sheet or less (slightly good, more than 5.0 pieces/sheet and 10.0 pieces or less in 50×100 mm)

D: Occurrence rate exceeds 10.0/sheet (failed, more than 10.0 out of 50×100mm)

The obtained analysis results and evaluation results are shown in Tables 5 and 6.

2. 8 Abrasiveness

In the above-mentioned polishing with #800 sandpaper for macro pattern observation, polishing was performed with a polishing time of 1 minute. If the surface skin is removed in 1 minute of polishing time, it is judged that the productivity of drum manufacturing is maintained, the abrasiveness is set to good (OK), and if the surface skin is not removed in 1 minute, the productivity of drum manufacturing is lowered. It was judged that it was not desirable (NG).

2. 9 shrink fit

The shrink fit property was evaluated as follows. The shrink fit property is affected by Young's modulus and aspect ratio (for example, in the case of a tube plate, the ratio of the outer diameter of the inner tube to the inner diameter of the outer tube). In particular, in order to obtain the stress required for fixing titanium, the larger the Young's modulus of titanium, the smaller the deformation amount can be achieved, so that the heating temperature can be lowered and workability is improved. Therefore, the case of 135 GPa or more in Young's modulus was said to be excellent in shrink fit property.

The obtained analysis results and evaluation results are shown in Tables 5 and 6. As shown in Tables 5 and 6, "angle θ is

The area ratio (%) of crystal grains that are 0° or more and 40° or less” is the area ratio of crystal grains whose angles between the c-axis of the α phase with respect to the plate thickness direction are 0° or more and 40° or less. In addition, "Al uniformity (%)" shown in Table 2 is the area ratio of the area|region whose Al density|concentration is ([Al%]-0.2) mass % or more and [Al%]+0.2) mass % or less. In addition, "RT" in "cold rolling process" shown in Table 2 means room temperature.

As shown in Tables 5 and 6, in the titanium alloy plates according to Inventive Examples 1 to 16 and 101 to 115, the macro pattern was suppressed. On the other hand, the titanium alloy plate which concerns on Comparative Examples 1-5 generate|occur|produced many macro patterns.

Moreover, in Invention Examples 1 to 16 with a low Al content, the generation of macro patterns was more suppressed compared to Invention Examples 101 to 115 with a high Al content. On the other hand, in Inventive Examples 101 to 115 in which the Al content was high, the Young's modulus was high and the shrink fit properties were excellent.

<Example 2>

Assuming application to a copper foil manufacturing drum, the titanium alloy plate obtained by the method similar to the invention example of the said Example 1 shown in Table 7 is used as a base material, After processing into the cylindrical shape of diameter 1m, butt part ( Two adjacent ends) were welded using the titanium wire for welding shown in Table 7. In the welding, the thickness of the preliminary brazing was set to 25% or less of the thickness of the base material. Then, only the pre-stitching was reduced to the thickness of the base material at a temperature of 200° C. or less after the pre-stitching. Finally, the welding part was heat-treated under the conditions of 600-800 degreeC and 20-90 minutes, and the welding sample by the titanium wire for welding concerning each invention example and each comparative example was obtained.

According to JIS G 0551:2013, the crystal grain diameter in the metal structure of the obtained weld part was measured based on the comparative method, and it obtained as a particle size number (GSN).

In addition, with respect to the metal structure of the weld zone, using SEM/EPMA, the concentration distribution of Fe or the β-phase stabilizing element is measured, and the concentration of Fe or the total concentration of the β-phase stabilizing element is 1 mass% higher than the average concentration of the measurement range. An abnormally high point (thickening part) was defined as a beta phase, and the area ratio was calculated|required. The area ratio and volume ratio were assumed to be equal, and the obtained area ratio was the volume ratio of the β phase, the area ratio of the portion (other than the enriched portion) where the β-phase stabilizing element was not concentrated was the volume ratio of the α phase, .

Moreover, the Vickers hardness (Hv) of the welding part in the welding sample which concerns on each obtained each invention example and each comparative example, and a base material was measured 3-5 points|pieces by 1 kg of load, and it computed with the average value. Using a contact-type roughness meter, according to JISB0633:2001, λc: 0.8 mm, λs: 2.5 μm, rtip: 2 μm, the step (μm) between the boundary between the weld and the base material was measured.

For the macro pattern of the weld zone in each obtained welding sample, the surface of each titanium alloy plate of 50 x 100 mm size of about 5 to 10 sheets is polished with #800 buffing, and a 10% nitric acid and 5% hydrofluoric acid solution is used. Thus, the surface was observed after corrosion. Next, the pattern of stripes generated with a length of 3 mm or more was made into a macro pattern, and evaluation was performed as follows according to the average of the occurrence ratios.

A: Occurrence rate is 1.0 or less per sheet (Very good, 1.0 or less in 50×100 mm)

B: Occurrence ratio exceeds 1.0/sheet and less than 5.0/sheet (good, more than 1.0 and 5.0 or less in 50×100 mm)

C: Occurrence rate of more than 5.0 pieces/sheet and 10.0 pieces/sheet or less (slightly good, more than 5.0 pieces/sheet and 10.0 pieces or less in 50×100 mm)

D: Occurrence rate exceeds 10.0/sheet (failed, more than 10.0 out of 50×100mm)

Also, a case where a step of 5 µm or more occurred at the boundary between the weld and the base material was evaluated as D in the macro-shaped column.

In addition, 10 points of each of the convex and concave portions in an arbitrary 50 cm section in the weld bead obtained by welding were measured with a dips gauge, and the average height of the upper three points of the convex portion was h, and the average of the lower three points of the concave portion When the height is D and the average height of 20 measurement points is A, the case where the values of (hA)/A and (AD)/A are both 0.3 or less is OK, and the case where it is 0.1 or less is Ex.

The results are shown in Table 8.

As shown in Table 8, in the invention examples 201 to 205, the generation of macro patterns of the welds was suppressed. On the other hand, in Comparative Examples 201 and 202, a large number of macro patterns of the welds were generated.

ADVANTAGE OF THE INVENTION According to this invention, when it uses for the drum for copper foil manufacture, it becomes possible to provide the copper foil manufacturing drum manufactured using the titanium alloy plate and copper titanium alloy plate which can suppress generation|occurrence|production of a macro pattern.

1: Copper foil manufacturing apparatus
2: electrodeposition drum
10: electrolyzer
30: electrode plate
40: winding unit
50: guide roll
60: winding roll
A: copper foil
20: copper foil manufacturing drum
21: inner drum
22: titanium alloy plate
23: weld

Claims (13)

in mass %,
Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, and Al: 0% or more and 7.0% or less one or two or more types: 0.2% or more and 7.0% or less in total;
N: 0.100% or less;
C: 0.080% or less;
H: 0.015% or less;
O: 0.700% or less, and
Fe: contains 0.500% or less,
the balance has a chemical composition containing Ti and impurities,
an average crystal grain size of 40 μm or less,
the standard deviation of the particle size distribution based on the logarithm of the crystal grain size in unit μm is 0.80 or less,
The crystal structure includes an α-phase that is a hexagonal closest packed structure,
The area ratio of crystal grains in which the [0001] direction of the α phase with respect to the plate thickness direction is 0° or more and 40° or less is 70% or more,
titanium alloy plate. The method according to claim 1, wherein in the (0001) pole figure from the normal direction of the plate surface, the expansion index of the pole figure using the spherical harmonic function method of the electron beam backscattering diffraction method is 16, and the Gaussian half width is 5°. The peak of the degree of integration calculated by texture analysis exists within 30° from the normal direction of the plate surface, and has a texture with a maximum degree of integration of 4.0 or more,
titanium alloy plate. The titanium alloy sheet according to claim 1 or 2, wherein the standard deviation of the particle size distribution is (0.35×lnD-0.42) or less when the average crystal grain size is D in unit μm. The ratio of the twin grain boundary length to the total grain boundary length of the plate thickness cross section at the position of 1/4 plate thickness from the surface when the plate|board thickness direction cross section is observed in any one of Claims 1-3. This 5.0% or less titanium alloy plate. According to any one of claims 1 to 4, in the chemical composition,
Sn: 0.2% or more and 2.0% or less,
Zr: 0.2% or more and 5.0% or less, and
Al: 0.2% or more and 5.0% or less of one type or two or more types constituted from the group consisting of 0.2% or more and 3.0% or less in total;
titanium alloy plate. According to any one of claims 1 to 4, in the chemical composition,
Al: contains more than 1.8% and 7.0% or less,
Vickers hardness of 350 Hv or less,
titanium alloy plate. The following formula (1) according to claim 6, wherein the Al content is [Al%], the Zr content is [Zr%], the Sn content is [Sn%], and the O content is [0%] by mass%. ) has an Al equivalent Aleq of 7.0 or less,
titanium alloy plate.
Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] Formula (1) The composition analysis according to claim 6 or 7, wherein an analysis area of 20 mm x 20 mm or more in a plane perpendicular to the plate thickness direction at a position of 1/4 plate thickness from the surface is analyzed using an electron beam microanalyzer, Assuming that the average content of Al is [Al%], the area ratio of the region in which the concentration of Al is ([Al%] -0.2) mass% or more and [Al%]+0.2) mass% or less with respect to the area of the analysis region is 90% or more, a titanium alloy plate. The titanium alloy plate according to any one of claims 1 to 8, wherein the α phase is contained in an amount of 98.0% by volume or more. The titanium alloy plate according to any one of claims 1 to 9, which is a titanium alloy plate for copper foil production drums. a cylindrical inner drum;
The titanium alloy plate according to any one of claims 1 to 10, which is adhered to the outer peripheral surface of the inner drum;
Welding portion provided in the butt portion of the titanium alloy plate
have,
The metal structure of the welded portion has an α phase of 98.0% or more by volume ratio, and is 6 or more and 11 or less by a particle size number based on JIS G 0551:2013,
Copper foil manufacturing drum. a welding process of welding two adjacent ends of a titanium alloy plate processed into a cylindrical shape using a welding titanium wire;
The titanium wire for welding is, in mass%,
At least one selected from the group consisting of Sn, Zr and Al: 0.2% or more and 6.0% or less in total;
O: 0.01% or more and 0.70% or less;
N: 0.100% or less;
C: 0.080% or less;
H: 0.015% or less, and
Fe: 0.500% or less,
the balance having a chemical composition comprising Ti and impurities
A method for manufacturing a copper foil manufacturing drum. The titanium wire for welding according to claim 12, wherein at least a part of the O exists as an oxide of one or more elements selected from the group consisting of Ti, Sn, Zr and Al.
A method for manufacturing a copper foil manufacturing drum.

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