WO2020213719A1 - チタン合金板、チタン合金板の製造方法、銅箔製造ドラム及び銅箔製造ドラムの製造方法 - Google Patents
チタン合金板、チタン合金板の製造方法、銅箔製造ドラム及び銅箔製造ドラムの製造方法 Download PDFInfo
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- WO2020213719A1 WO2020213719A1 PCT/JP2020/016899 JP2020016899W WO2020213719A1 WO 2020213719 A1 WO2020213719 A1 WO 2020213719A1 JP 2020016899 W JP2020016899 W JP 2020016899W WO 2020213719 A1 WO2020213719 A1 WO 2020213719A1
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- titanium alloy
- alloy plate
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- copper foil
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 272
- 238000004519 manufacturing process Methods 0.000 title claims description 122
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 116
- 239000011889 copper foil Substances 0.000 title claims description 112
- 239000013078 crystal Substances 0.000 claims abstract description 210
- 239000010936 titanium Substances 0.000 claims abstract description 82
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000009826 distribution Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 99
- 238000000034 method Methods 0.000 claims description 72
- 238000003466 welding Methods 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 229910052726 zirconium Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 29
- 230000010354 integration Effects 0.000 claims description 28
- 229910052718 tin Inorganic materials 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 21
- 238000004458 analytical method Methods 0.000 claims description 20
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000005520 cutting process Methods 0.000 description 8
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- 238000005259 measurement Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000010953 base metal Substances 0.000 description 6
- 238000005422 blasting Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 229910052802 copper Inorganic materials 0.000 description 4
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- 239000007769 metal material Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- 229910045601 alloy Inorganic materials 0.000 description 3
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- 238000005554 pickling Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B3/02—Rolling special iron alloys, e.g. stainless steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/325—Ti as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
Definitions
- the present invention relates to a titanium alloy plate, a method for manufacturing a titanium alloy plate, a copper foil manufacturing drum, and a method for manufacturing a copper foil manufacturing drum.
- This application claims priority based on Japanese Patent Application No. 2019-078824 filed in Japan on April 17, 2019 and Japanese Patent Application No. 2019-078288 filed in Japan on April 17, 2019. And the contents are used here.
- Copper foil is often used as a raw material for wiring of wiring boards such as multi-layer wiring boards and flexible wiring boards, and for conductive parts of electronic components such as current collectors of lithium ion batteries.
- FIG. 7 is a schematic view of a copper foil manufacturing apparatus.
- the copper foil manufacturing apparatus 1 is, for example, as shown in FIG. 7, an electrolytic cell 10 in which a copper sulfate solution is stored and an electric electrode provided in the electrolytic cell 10 so that a part of the copper sulfate solution is immersed in the copper sulfate solution. It includes a landing drum 2 and an electrode plate 30 which is immersed in a copper sulfate solution in an electrolytic cell 10 and is provided so as to face the outer peripheral surface of the electrodeposition drum 2 at predetermined intervals.
- the copper foil A is electrodeposited on the outer peripheral surface of the electrodeposition drum 2 to be generated.
- the copper foil A having a predetermined thickness is peeled off from the electrodeposition drum 2 by the take-up portion 40, and is taken up by the take-up roll 60 while being guided by the guide roll 50.
- titanium As a material for a drum (electrodeposition drum), titanium is generally used for its surface (outer peripheral surface) from the viewpoints of excellent corrosion resistance and excellent peelability of copper foil.
- the surface of the titanium material constituting the drum is gradually corroded in the copper sulfate solution. Then, the state of the corroded drum surface can be transferred to the copper foil during the production of the copper foil.
- the corrosion state and degree of corrosion of a metal material differ depending on various internal factors caused by the metal structure such as crystal structure, crystal orientation, defects, segregation, processing strain, and residual strain of the metal material.
- the homogeneous surface state of the drum cannot be maintained, and a heterogeneous surface is generated on the drum surface.
- the inhomogeneous surface generated on the drum surface can be identified as a pattern.
- a pattern caused by a macrostructure having a relatively large area and which can be discriminated with the naked eye 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.
- the macrostructure of the titanium material constituting the drum is homogenized, and the corrosion on the surface of the drum is homogenized, so that the macrostructure is inhomogeneous. It is important to reduce the macro pattern caused by.
- Patent Document 1 contains Cu: 0.15% or more and less than 0.5%, oxygen: more than 0.05%, 0.20% or less, Fe: 0.04% or less in mass%, and the balance of titanium.
- a titanium plate for an electrolytic Cu foil manufacturing drum has been proposed, which is composed of unavoidable impurities and has an ⁇ -phase homogeneous fine recrystallization structure having an average crystal grain size of less than 35 ⁇ m.
- Patent Document 2 contains Cu: 0.3 to 1.1%, Fe: 0.04% or less, oxygen: 0.1% or less, hydrogen: 0.006% or less in mass%, and average crystal grains.
- the texture is ⁇ -phase (0001) from the rolling surface in the normal direction (ND axis).
- the tilt angle of the normal of the (0001) plane is within the range of an ellipse with ⁇ 45 ° in the rolling width direction TD direction as the major axis and ⁇ 25 ° in the final rolling direction RD direction as the minor axis.
- a titanium plate for an electrolytic Cu foil manufacturing drum is proposed, wherein the total area of the crystal grains existing in is A, the total area of the other crystal grains is B, and the area ratio A / B is 3.0 or more. Has been done.
- Patent Document 3 contains Al: 0.4 to 1.8%, and has an average crystal grain size of 4 mm or more, 1.0 mm below the surface, and a portion parallel to the plate surface of 1/2 plate thickness. 2 or more, Vickers hardness 115 or more and 145 or less, the texture is the TD (0001) plane in the normal ND rolling width direction of the final rolling direction RD rolling surface at the portion parallel to the plate surface extending from 1 mm below the surface to 1/2 plate thickness.
- the tilt angle of the c-axis in the TD direction in the (0001) plane pole diagram of the ⁇ phase from the normal direction from the rolled surface is -45 to 45 °, and the c-axis RD direction.
- the total area of the crystal grains having the c-axis in the elliptical region where the tilt angle to is -25 to 25 ° is A, the total area of the other crystal grains is B, and the area ratio A / B is 3. Titanium alloy thick plates of 0 or more have been proposed.
- Patent Document 4 describes that when a titanium and a titanium alloy plate are manufactured by a method including a step of sequentially performing lump forging, coarse heat rolling and finishing hot rolling, the heating temperature in the lump forging and rough heat rolling is 950 ° C. or higher. It has a uniform and fine macro pattern, which is characterized in that the heating temperature in the finishing hot rolling is 700 ° C. or less, and the cross hot rolling in which the rolling directions of the rough hot rolling and the finishing hot rolling are changed is performed. A method for producing titanium and a titanium alloy plate has been proposed.
- Patent Document 5 describes a titanium cathode electrode made of a titanium material used when obtaining an electrolytic copper foil using a copper electrolytic solution, wherein the titanium material has a crystal grain size number of 7.0 or more and contains initial hydrogen.
- a titanium cathode electrode for producing an electrolytic copper foil characterized in that the amount is 35 ppm or less, has been proposed. According to Patent Document 5, if this titanium cathode electrode is used, it can be used for an extremely long period of time in the production of electrolytic copper foil, the number of maintenances can be effectively reduced, and a high quality electrolytic copper foil can be produced for a long period of time. It is disclosed that it will be possible to manufacture across.
- Patent Document 6 includes Cu: 0.5 to 2.1%, Ru: 0.05 to 1.00%, Fe: 0.04% or less, and oxygen: 0.10% or less in mass%.
- a titanium plate for an electrolytic Cu foil manufacturing drum which is composed of a residual titanium and unavoidable impurities and has a homogeneous fine recrystallized structure, has been proposed.
- the drum used for manufacturing the copper foil is manufactured by shrink-fitting an insoluble metal plate such as a titanium plate on the surface of the core material which is the core of the copper foil manufacturing drum.
- the plate to be shrink-fitted on the surface of the core material is preferably a plate having excellent shrink-fitting property.
- the copper foil manufacturing drum described above is manufactured by bending a titanium plate into a cylindrical shape and welding adjacent ends.
- the latter method is suitable for producing a high-quality copper foil production drum because it is easy to control the metal structure of the titanium plate.
- By homogenizing the macrostructure of the titanium material constituting the copper foil manufacturing drum and achieving homogeneous corrosion of the drum it is possible to reduce the macro pattern caused by the inhomogeneous macrostructure.
- the metal structure of the welded part of the drum manufactured by welding is inevitably different from that of other parts, even if the macrostructure of the titanium material used as the surface material of the copper foil manufacturing drum is made uniform. , There is a problem that a macro pattern caused by a welded portion is likely to occur.
- the proportion of welded parts on the surface of the copper foil manufacturing drum is not large, in recent years there has been an increasing demand for reducing the macro pattern of the welded parts.
- Patent Document 7 describes for molten metal formation in which a Ti-based oxide film having a predetermined tensile strength in the longitudinal direction of the wire rod and having a thickness of 1 ⁇ m or more and 5 ⁇ m or less is formed on the surface of the wire rod main body.
- Ti-based wire rods have been proposed.
- Patent Document 8 describes a welding wire made of Ti or a Ti alloy, which has an oxygen-enriched layer on its surface and further has a metal compound having at least one metal selected from the group of alkali metals and alkaline earth metals. Has been proposed.
- Patent Documents 7 and 8 are not intended to improve welding and the structure of welded portions in the production of copper foil manufacturing titanium drums. Therefore, it is difficult to suppress the macro pattern using the same technique. That is, a titanium rod wire for welding, which is used in the production of a titanium drum produced by copper foil and can suppress the occurrence of macro patterns in the welded portion of the titanium drum produced by copper foil, has not been sufficiently studied.
- Japanese Patent Application Laid-Open No. 2009-41064 Japanese Patent Application Laid-Open No. 2012-112017 Japanese Patent Application Laid-Open No. 2013-7063 Japanese Patent Application Laid-Open No. 60-9866 Japanese Patent Application Laid-Open No. 2002-194585 Japanese Patent Application Laid-Open No. 2005-298853 Japanese Patent Application Laid-Open No. 2005-21983 Japanese Patent Application 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 use a titanium alloy plate and a titanium alloy plate capable of suppressing the generation of macro patterns when used in a drum for producing copper foil.
- a preferred object of the present invention is to use a titanium alloy plate and a titanium alloy plate which can suppress the generation of macro patterns when used in a drum for producing copper foil and have excellent shrink fit. To provide copper foil manufacturing drums.
- Another preferred object of the present invention is to produce a copper foil using a titanium wire rod for welding, which is used in the production of a copper foil manufacturing titanium drum and can suppress the occurrence of macro patterns in the welded portion of the copper foil manufacturing titanium drum. It is an object of the present invention to provide a method for manufacturing a drum and a copper foil manufacturing drum.
- the present inventors have diligently studied to solve the above-mentioned problems. As a result, simply reducing the grain size of the texture of the texture in the titanium material or making the normal of the (0001) plane of the crystal close to perpendicular to the rolled plane (plate surface) is macroscopic to the level required this time. It was found that the occurrence of patterns could not be suppressed.
- the chemical composition is set to a chemical composition in which the precipitation of ⁇ phase is suppressed, and the crystal grains are made not only fine but also uniform in size in the structure, and the structure is hexagonal close-packed.
- the area ratio of crystal grains containing the ⁇ phase, which is a close-packed structure, and the angle formed by the ⁇ phase in the [0001] direction (c-axis) with respect to the plate thickness direction is 0 ° or more and 40 ° or less is set to 70% or more, more preferably In the (0001) pole diagram from the normal direction of the plate surface, the peak of the degree of accumulation of crystal grains exists within 30 ° from the normal direction of the plate surface, and the maximum degree of integration is 4.0 or more. It was found that the occurrence of macro patterns can be suppressed by controlling the structure so that it becomes an aggregate structure. Then, they have found a method for producing a titanium alloy plate capable of simultaneously achieving such a chemical composition and texture, and have reached the present invention.
- the present inventors have also studied the shrinkage fit of a titanium alloy plate into a core material in the production of a copper foil production drum. As a result, it was found that the Young's modulus of the titanium alloy plate affects the shrink fit. Based on this finding, the present inventors focused on the hardness, grain size, crystal orientation, second phase, and element distribution of the titanium alloy plate. As a result, when Al is contained in a larger amount than the titanium alloy plate used for a drum for general copper foil production, grain growth is suppressed and a fine structure is easily formed, and the hardness of the titanium alloy plate is increased. At the same time, it was found that the Young's modulus of the titanium alloy plate is improved.
- the present inventors have studied the suppression of the occurrence of macro patterns in welded parts. As a result, it was found that it is possible to suppress the occurrence of macro patterns in the welded portion by making the metal structure of the welded portion mainly of ⁇ phase, making the crystal grains finer and controlling the hardness. Further, in order to obtain the structure of such a welded portion, it is effective to include an appropriate amount of one or more selected from the group consisting of Sn, Zr and Al and O in the titanium wire for welding. I found that there is.
- the gist of the present invention completed based on the above findings is as follows.
- the titanium alloy plate according to one aspect of the present invention has 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 in mass%. 1 type or 2 types or more composed of a group consisting of% or less: 0.2% or more and 7.0% or less in total, N: 0.100% or less, C: 0.080% or less, H: 0. It has a chemical composition containing 015% or less, O: 0.700% or less, and Fe: 0.500% or less, the balance containing Ti and impurities, and has an average crystal grain size of 40 ⁇ m or less.
- the standard deviation of the grain size distribution based on the logarithmic grain size in the unit ⁇ m is 0.80 or less
- the crystal structure includes an ⁇ phase having a hexagonal close-packed structure
- the ⁇ phase [0001] with respect to the plate thickness direction.
- the area ratio of the crystal grains having an angle of 0 ° or more and 40 ° or less in the direction is 70% or more.
- the titanium alloy plate according to the above [1] has an expansion index of the pole diagram using the spherical harmonic method of the electron backscatter diffraction method in the (0001) pole diagram from the normal direction of the plate surface. 16.
- the titanium alloy plate according to any one of [1] to [3] above has a total grain boundary of the plate thickness cross section at a position of 1/4 of the plate thickness from the surface when the plate thickness direction cross section is observed.
- the ratio of the twin grain boundary length to the length may be 5.0% or less.
- the titanium alloy plate according to any one of [1] to [4] above has Sn: 0.2% or more and 2.0% or less and Zr: 0.2% or more and 5.0 in the chemical composition. 1 type or 2 types or more composed of a group consisting of% or less and Al: 0.2% or more and 3.0% or less may be contained in a total of 0.2% or more and 5.0% or less.
- 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 has a Vickers hardness of 350 Hv or less. There may be.
- the titanium alloy plate according to the above [6] has an Al content of [Al%], a Zr content of [Zr%], a Sn content of [Sn%], and an O content in mass%.
- the Al equivalent Aleq represented by the following formula (1) may be 7.0 or less.
- Aleq [Al%] + [Zr%] / 6 + [Sn%] / 3 + 10 ⁇ [O%] Equation (1)
- the titanium alloy plate according to [6] or [7] above is analyzed using an electron probe microanalyzer on a surface 20 mm ⁇ 20 mm or more perpendicular to the plate thickness direction at a position 1/4 of the plate thickness from the surface.
- the titanium alloy plate according to any one of [1] to [8] above may contain 98.0% by volume or more of the ⁇ phase.
- the titanium alloy plate according to any one of [1] to [9] above may be a titanium alloy plate for a copper foil manufacturing drum.
- the copper foil manufacturing drum according to another aspect of the present invention includes a cylindrical inner drum and titanium according to any one of [1] to [10], which is adhered to the outer peripheral surface of the inner drum. It has an alloy plate and a welded portion provided at a butt portion of the titanium alloy plate, and the metal structure of the welded portion has an ⁇ phase of 98.0% or more in terms of volume ratio, and JIS G 0551 : A particle size number based on 2013, which is 6 or more and 11 or less.
- a method for manufacturing a copper foil manufacturing drum according to another aspect of the present invention includes a welding step of welding two adjacent ends of a titanium alloy plate processed into a cylindrical shape using a titanium wire for welding.
- the titanium wire for welding is one or more selected from the group consisting of Sn, Zr and Al in mass%: 0.2% or more and 6.0% or less in total, O: 0.01% or more and 0. Chemical composition containing .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 containing Ti and impurities.
- the method for manufacturing a copper foil manufacturing drum according to the above [12] is one type in which at least a part of the O is selected from the group consisting of Ti, Sn, Zr and Al in the titanium wire rod for welding. It may exist as an oxide of the above elements.
- a titanium alloy plate capable of suppressing the generation of macro patterns when used in a drum for producing copper foil, and a copper foil production drum produced by using the titanium alloy plate. It becomes possible. Further, according to a preferred embodiment of the present invention, it is possible to provide a titanium alloy plate which can suppress the generation of macro patterns when used in a drum for producing a copper foil and has excellent shrink fit. Further, according to a preferred embodiment of the present invention, it is possible to provide a method for manufacturing a copper foil manufacturing drum and a copper foil manufacturing drum that suppress the generation of macro patterns in a welded portion of the copper foil manufacturing drum.
- Titanium alloy plate > First, the titanium alloy plate according to the present embodiment will be described.
- the titanium alloy plate according to this embodiment is assumed to be used as a material for a drum for producing copper foil (copper foil manufacturing drum). Therefore, it can be said that the titanium alloy plate according to the present embodiment is a titanium alloy plate for a copper foil manufacturing drum. When used in a copper foil manufacturing drum, one side of the titanium alloy plate constitutes the cylindrical surface of the drum.
- the titanium alloy plate according to the present embodiment is composed 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 in mass%. 1 type or 2 types or more composed of groups, 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, It contains O: 0.700% or less and Fe: 0.500% or less, and the balance contains Ti and impurities. In the following, unless otherwise specified, the notation of "%" regarding the chemical composition shall represent "mass%".
- Industrial pure titanium has an extremely small amount of additive elements, and the structure is substantially ⁇ -phase and single-phase. If such a titanium alloy plate made of pure titanium for industrial use is used for the drum, the drum is uniformly corroded when the drum is immersed in the copper sulfate solution. As a result, the generation of macro patterns due to the difference in the corrosion rate between the ⁇ phase and the ⁇ phase is suppressed.
- the titanium alloy plate according to the present embodiment is substantially ⁇ -phase single-phase industrial pure titanium, in terms of mass%, Sn: 0% or more and 2.0% or less, Zr: 0% or more and 5.0% or less, And Al: 1 type or 2 types or more composed of a group consisting of 0% or more and 7.0% or less, so as to be 0.2% or more and 7.0% or less in total. .. The reason for limiting the content of each element will be described.
- the Al content is preferably 0.2% or more and 3.0% or less, and the total content of one or more selected from the group consisting of Sn, Zr and Al. Is 0.5% or more and 5.0% or less.
- the total content of one or more selected from the group consisting of Sn, Zr and Al is more preferably 0.5% or more and 4.0% or less.
- Sn is a neutral element and is an element that suppresses crystal grain growth by being dissolved in titanium.
- the Sn content is preferably 0.2% or more.
- the Sn content is more preferably 0.3% or more.
- Sn is dissolved in the ⁇ phase and ⁇ phase in titanium to stabilize each phase. If the Sn content is too high, the high-temperature strength becomes high, and the reaction force during hot rolling distorts the plate shape after hot rolling and tends to form a wavy shape. Dislocations are introduced into the crystals of the titanium alloy plate by applying strain to the wavy titanium alloy plate by processing to correct the shape. Due to this dislocation, macro patterns are likely to occur.
- the Sn content is preferably 2.0% or less, more preferably 1.5% or less. Since Sn is not essential in the titanium alloy plate, the Sn content may be 0% when Zr and / or Al is contained in an amount of 0.2% or more in total.
- Zr is a neutral element, and is an element that suppresses crystal grain growth by being dissolved in titanium.
- the Zr content is preferably 0.2% or more.
- the Zr content is more preferably 0.3% or more.
- Zr is an element that stabilizes each phase by being dissolved in the ⁇ phase and ⁇ phase in titanium. If the Zr content is too high, the temperature range in which the two phases of the ⁇ phase and the ⁇ phase are thermally stable becomes wide, and the ⁇ phase tends to precipitate during heating.
- the ⁇ phase corrodes preferentially over the ⁇ phase
- the ⁇ phase is preferentially corroded and macroscopically appears on the drum surface.
- a pattern occurs.
- the macro pattern may be transferred to the copper foil.
- the Zr content is 5.0% or less.
- the Zr content is preferably 4.5% or less, more preferably 4.0%.
- the Zr content is more preferably 2.5% or less, still more preferably 2.0% or less. Since Zr is not essential in the titanium alloy plate, the Zr content may be 0% when Sn and / or Al is contained in an amount of 0.2% or more in total.
- Al is an ⁇ -phase stabilizing element and suppresses grain growth in heat treatment in an ⁇ -phase single-phase temperature range, similarly to Sn and Zr.
- the Al content is preferably 0.2% or more.
- the Al content is more preferably 0.5% or more.
- Al is also an element that increases Young's modulus of the titanium alloy plate. By increasing the Young's modulus, in the production of the copper foil manufacturing drum, the shrink fit property when the core material and the titanium alloy plate are shrink fit is improved. This improves the productivity of the copper foil manufacturing drum. Further, by increasing the Young's modulus, the titanium alloy plate is uniformly shrink-fitted and the polishability of the titanium alloy plate is improved.
- the Al content is preferably more than 1.8%.
- Al further increases the high temperature strength of the titanium alloy plate as compared with Sn or Zr. As will be described later, when the titanium alloy plate according to the present embodiment is manufactured, hot rolling is carried out to a relatively low temperature for the purpose of controlling the texture. Therefore, if the high-temperature strength becomes too high, the reaction force during hot rolling becomes large, the shape of the titanium alloy plate after hot rolling is greatly distorted, and the titanium alloy plate becomes wavy.
- the Al content is set to 7.0% or less. From the above viewpoint, the Al content is preferably 3.0% or less, more preferably 2.5% or less. Since Al is not essential in the titanium alloy plate, the Al content may be 0% when Sn and / or Zr are contained in a total of 0.2% or more.
- the concentration distribution of Al should be small.
- the Al content is more than 1.8% and the Al content (average content) is [Al%]
- the Al concentration is ([Al%]. ] -0.2) Mass% or more ([Al%] +0.2) mass% or less
- the area ratio of the region is preferably 90% or more.
- the segregation of Al is evaluated by using an electron probe microanalyzer (EPMA) with a beam diameter of 500 ⁇ m and a step size of 500 ⁇ m, which is the same as the beam diameter. It is performed by analyzing the composition of a region of 20 mm ⁇ 20 mm or more at the position of 4. In order to convert the composition analysis result into the alloy element concentration, the average chemical composition and the intensity of K ⁇ ray of JIS Class 1 industrial pure titanium and the target titanium alloy plate are analyzed, and linear approximation is obtained from the result. A calibration curve is used.
- EPMA electron probe microanalyzer
- the Al content is [Al%] (mass%)
- the Zr content is [Zr%] (mass%)
- the Sn content is [Sn%] (mass%)
- the Al equivalent Aleq represented by the following formula (1) is preferably 7.0 (mass%) or less.
- Aleq [Al%] + [Zr%] / 6 + [Sn%] / 3 + 10 ⁇ [O%] Equation (1)
- the Al equivalent is an index indicating the degree of stabilization of the ⁇ phase, and as the Al equivalent increases, the hardness increases while the toughness decreases. By setting the Al equivalent to 7.0% by mass or less, the toughness can be maintained and the shrink fit can be improved.
- O is an element that contributes to the improvement of the strength of the titanium alloy plate and the increase of the surface hardness.
- the O content is set to 0.700% or less.
- the O content is preferably 0.400% or less.
- the O content is more preferably 0.150% or less, still more preferably 0.120% or less. Since O is not essential in the titanium alloy plate, the lower limit of its content is 0%. However, it is difficult to prevent contamination from titanium sponge, which is a dissolving raw material, and additive elements, and the practical lower limit is 0.020%.
- the O content is preferably 0.030% or more.
- Fe is an element that reinforces the ⁇ phase.
- the upper limit of the Fe content is set to 0.500%.
- the Fe content is preferably 0.100% or less, more preferably 0.080% or less. Since Fe is not essential in the titanium alloy plate, the lower limit of its content is 0%. However, it is difficult to prevent Fe from being mixed in the actual production, and the practical lower limit is 0.001%.
- the titanium alloy plate according to the present embodiment may further contain N, C, or H as impurities.
- N is an element that forms a nitride with Ti. When the nitride is formed, the titanium alloy plate may be hardened or embrittled. Therefore, it is preferable to suppress the content of N as much as possible.
- the N content is 0.100% or less.
- the N content is preferably 0.080% or less. Since N is not essential in the titanium alloy plate, the lower limit of its content is 0%. However, N is an impurity mixed in during the manufacturing process, and the lower limit of the substantial N content may be 0.0001%.
- C is an element that forms carbides together with Ti and hardens or embrittles the titanium alloy plate in the same way as nitrides.
- the C content is preferably as low as possible in order to suppress hardening and embrittlement of the titanium alloy plate.
- the C content is 0.080% or less.
- the C content is preferably 0.050% or less. Since C is not essential in the titanium alloy plate, the lower limit of its 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 0.0005%.
- H is an element that forms a hydride together with Ti. When hydrides are formed, the titanium alloy plate may become embrittled. In addition, macro patterns may occur due to hydrides. Therefore, it is preferable to suppress the H content as much as possible.
- the H content is 0.015% or less.
- the H content is preferably 0.010% or less. Since H is not essential in the titanium alloy plate, the lower limit of its 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 0.0005%.
- the balance of the chemical composition of the titanium alloy plate according to the present embodiment contains Ti and impurities, and may consist of Ti and impurities.
- Impurities are Cl, Na, Mg, Si, Ca mixed in the refining process and Mo, Nb, Ta, V, Cr, Mn, Co, Ni mixed in from scrap, to give a specific example other than the above-mentioned elements. , Cu and the like.
- the total content of impurities is 0.50% or less.
- the above impurities may include ⁇ -phase stabilizing elements. Since a large amount of ⁇ -phase precipitation affects the generation of macro patterns, it is preferable that the amount of ⁇ -phase stabilizing elements is small.
- the ⁇ -phase stabilizing element examples include V, Mo, Ta, Nb, Cr, Mn, Co, Ni, Cu and the like.
- the total content of impurities is 0.50% or less, and the content of each ⁇ -phase stabilizing element contained in the titanium alloy plate is 0.10% or less. Is more preferable.
- the chemical composition is determined by the following method.
- ⁇ -stabilizing elements such as Al, Zr, Sn, Fe, V, Mo, Ta, Nb, Cr, Mn, Co, Ni and Cu can be measured by IPC emission spectrum analysis.
- O and N can be measured by the inert gas melting, thermal conductivity / infrared absorption method using an oxygen / nitrogen simultaneous analyzer.
- C can be measured by an infrared absorption method using a carbon-sulfur simultaneous analyzer.
- H can be measured by the melting of an inert gas and the infrared absorption method.
- the titanium alloy plate according to the present embodiment has an average crystal grain size of 40 ⁇ m or less, a standard deviation of the grain size distribution based on the logarithmic grain size ( ⁇ m) of 0.80 or less, and a hexagonal close-packed crystal structure.
- the area ratio of crystal grains including the ⁇ phase, which is a packed structure, and the angle formed by the ⁇ phase in the [0001] direction with respect to the plate thickness direction is 0 ° or more and 40 ° or less is 70% or more.
- the metallographic structure of the titanium alloy plate according to the present embodiment will be described in detail step by step.
- the metallographic structure of the titanium alloy plate according to the present embodiment includes an ⁇ phase having a hexagonal close-packed structure.
- the metallographic structure of the titanium alloy plate according to the present embodiment may contain a ⁇ phase in addition to the ⁇ phase.
- the ⁇ phase corrodes in preference to the ⁇ phase. Therefore, when a titanium drum having a titanium alloy plate containing a ⁇ phase on the surface is used for producing a copper foil, the ⁇ phase is preferentially corroded to generate a macro pattern on the drum surface, and the macro pattern appears on the copper foil. May be transcribed. Further, when the ⁇ phase is aggregated and formed, the texture of the titanium alloy plate may change. Therefore, it is better to have less ⁇ phase.
- the volume fraction of the ⁇ phase in the titanium alloy plate according to the present embodiment is preferably 98.0% or more, more preferably 99.0% or more, and further preferably 100% ( ⁇ phase single phase). ).
- the metal structure of the titanium alloy plate does not include an unrecrystallized portion. Such unrecrystallized portions are generally coarse and can cause macro patterns. Therefore, the metal structure of the titanium alloy plate is preferably a completely recrystallized structure.
- the recrystallized structure is a structure composed of crystal grains having an aspect ratio of less than 2.0. The presence or absence of unrecrystallized grains can be confirmed by the following method. That is, the crystal grains having an aspect ratio of 2.0 or more are regarded as unrecrystallized grains, and the presence or absence thereof is confirmed.
- a cross section obtained by cutting a titanium alloy plate is chemically polished, and an electron backscatter diffraction method; EBSD (Electron Backscattering Diffraction Pattern) is used to cover a region of 1 to 2 mm ⁇ 1 to 2 mm to 1 to 2 ⁇ m.
- EBSD Electro Backscattering Diffraction Pattern
- step 1 measure about 2 to 10 fields.
- the azimuth difference boundary of 5 ° or more measured by EBSD is defined as the crystal grain boundary
- the range surrounded by the crystal grain boundary is defined as the crystal grain
- the major axis and the minor axis of the crystal grain are obtained, and the major axis is the minor axis.
- the value divided by (major axis / minor axis) is calculated as the aspect ratio.
- the long axis is the line segment connecting any two points on the grain boundary of the ⁇ phase with the maximum length
- the short axis is orthogonal to the long axis and on the grain boundary.
- the volume ratio of each phase constituting the metal structure of the titanium alloy plate can be easily measured and calculated by the EPMA (Electron Probe Micronalizer) (SEM / EPMA) attached to the SEM (Scanning Electron Microscopy). Specifically, the arbitrary cross section of the plate is polished to a mirror surface, and at a magnification of 100 times, a 1 mm ⁇ 1 mm region at a position 1/4 of the plate thickness from the surface is formed in steps of 1 to 2 ⁇ m. The concentration distribution of Fe or other ⁇ -phase stabilizing elements is measured using SEM / EPMA for about 5 fields of view.
- EPMA Electron Micronalizer
- a point (concentrated portion) in which the concentration of Fe or the total concentration of ⁇ -phase stabilizing elements is 1 mass% or more higher than the average concentration in the measurement range is defined as ⁇ -phase, and the area ratio is obtained. Assuming that the area fraction and the volume fraction are equal, the obtained area fraction is defined as the volume fraction of ⁇ phase, and the area fraction of the portion where the ⁇ phase stabilizing element is not concentrated (other than the concentrated portion) is defined as the volume fraction of ⁇ phase. ..
- the average particle size and the particle size distribution of the crystal grains contained in the metal structure of the titanium alloy plate according to the present embodiment will be described.
- the grain size (crystal grain size) of the crystal grains of the metal structure of the titanium alloy plate is coarse, the crystal grains themselves become a pattern and the pattern is transferred to the copper foil, so the crystal grain size is finer. Is good.
- the average crystal grain size of the crystal grains of the metal structure of the titanium alloy plate exceeds 40 ⁇ m, the crystal grains themselves become a pattern and the pattern is transferred to the copper foil. Therefore, the average crystal grain size of the crystal grains of the metal structure of the titanium alloy plate is set to 40 ⁇ m or less.
- the average crystal grain size of the crystal grains of the metal structure of the titanium alloy plate is preferably 38 ⁇ m or less, more preferably 35 ⁇ m or less.
- the lower limit of the average crystal grain size of the crystal grains of the metal structure of the titanium alloy plate is not particularly limited. However, if the crystal grains are very small, unrecrystallized portions may be generated during the heat treatment. Therefore, the average crystal grain size of the crystal grains is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
- the average crystal grain size of the ⁇ phase is preferably 0.5 ⁇ m or less.
- the particle size of the ⁇ phase is large, large irregularities may be formed on the titanium alloy plate due to corrosion or polishing.
- the average crystal grain size of the ⁇ phase is 0.5 ⁇ m or less, it is possible to suppress the formation of irregularities due to corrosion and polishing.
- the present inventors have found that the macro pattern cannot be sufficiently suppressed only by the crystal grains of the metal structure of the titanium alloy plate being simply fine. That is, even if the crystal grains of the metal structure of the titanium alloy plate are fine, if the particle size distribution is wide, coarse crystal grains are present. If there is a portion where such coarse crystal grains and fine crystal grains coexist, a macro pattern may occur due to the difference in particle size. Therefore, it is important that the crystal grains of the metal structure of the titanium alloy plate are not only fine but also have a narrow particle size distribution, that is, a uniform grain size of the crystal grains is important for suppressing the occurrence of macro patterns. The present inventors have found.
- the standard deviation of the particle size distribution based on the logarithm of each crystal grain size ( ⁇ m) is 0.80 or less.
- the crystal grains satisfy the standard deviation of such a particle size distribution together with the average particle size as described above the crystal grains in the metal structure become sufficiently fine and uniform. As a result, when the titanium alloy plate is used for the drum, the generation of macro patterns is suppressed.
- the standard deviation of the grain size distribution based on the logarithm of the grain grain size ( ⁇ m) is preferably less than or equal to the threshold value (0.35 ⁇ lnD ⁇ 0.42) when the average grain size is D ( ⁇ m). ..
- the standard deviation ⁇ in the lognormal distribution can be calculated from the grain size distribution.
- the standard deviation ⁇ of the distribution of the conversion value obtained by converting the circle-equivalent particle size D of each crystal grain into the natural logarithm lnD is obtained. It is generally known that the grain size distribution of a metal material follows a lognormal distribution. Therefore, in calculating the standard deviation of the particle size distribution as described above, the obtained particle size distribution may be standardized to a lognormal distribution, and the standard deviation may be calculated from the standardized lognormal distribution.
- the crystal structure of the ⁇ phase of titanium has a hexagonal close-packed structure (hcp). Titanium having an hcp structure has a large anisotropy of physical properties depending on the crystal orientation. Specifically, titanium having an hcp structure has a high strength in a direction parallel to the [0001] direction (hereinafter, also referred to as a c-axis direction), and a low strength as it approaches a direction perpendicular to the c-axis direction.
- 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 are generated, the workability between the two aggregates is different, so that the copper foil At the time of manufacturing a manufacturing drum, the processability at the time of polishing may be different.
- the obtained drum may be recognized as a macro pattern having a size close to that of crystal grains. Therefore, it is preferable to suppress the occurrence of macro patterns by accumulating the crystal orientations of the texture of the titanium alloy plate as much as possible.
- titanium with an hcp structure has high strength in the direction parallel to the c-axis direction. Therefore, when the surface perpendicular to the c-axis is polished, the pattern after polishing is unlikely to occur. From this point of view, the crystal orientation of the texture of the titanium alloy plate should be perpendicular to the polished surface, that is, the thickness direction perpendicular to the surface of the titanium alloy plate (normal direction of the plate surface: ND). It is preferable to arrange the c-axis of the crystal lattice of the titanium alloy plate so as to be parallel.
- the area ratio of the crystal grains having an angle ⁇ formed by the normal direction (ND) of the plate surface and the c-axis of the ⁇ phase ([0001] direction) is 40 ° or less is all. It is 70% or more with respect to the area of the crystal grains of.
- the angle ⁇ is the angle shown in FIG.
- the area ratio of the crystal grains having an angle ⁇ of 40 ° or less is preferably 72% or more with respect to the area ratio of all the crystal grains. The higher the area ratio, the better. Therefore, although the upper limit of the area ratio is not set, it is practically possible to manufacture up to about 95%.
- the angle ⁇ formed by the c-axis of the ⁇ phase with respect to the plate thickness direction can be calculated by using the (0001) pole figure from the normal direction (ND) of the plate surface.
- the pole figure is obtained by chemically polishing the observation surface of the sample of the titanium alloy plate and analyzing the crystal orientation using EBSD. Specifically, for example, by scanning a region of 1 to 2 mm ⁇ 1 to 2 mm at intervals of 1 to 2 ⁇ m using EBSD, a crystal orientation map as shown in FIG. 5 can be obtained. For example, the region G1 shown in white in FIG.
- the region R1 surrounded by the dotted line b1 is a region where the angle ⁇ formed by the plate thickness direction (ND) and the c-axis of the crystal grain is 40 ° or less, and is a dotted line.
- the region R2 surrounded by b1 and the dotted line b2 is a region having an angle ⁇ of more than 40 ° and less than 60 °, and the region outside the dotted line b2 is a region having an angle ⁇ of 60 ° or more and 90 ° or less.
- the area ratio of crystal grains having an angle ⁇ formed by the thickness direction (ND) of the titanium alloy plate and the c-axis of the ⁇ phase of 40 ° or less can be calculated as follows.
- the cross section of the titanium alloy plate is chemically polished and crystal orientation analysis is performed using EBSD.
- a region of 1 to 2 mm ⁇ 1 to 2 mm is measured in steps of 1 to 2 ⁇ m for about 2 to 10 visual fields.
- measurement point data in which the angle between the ND and the c-axis is 40 ° or less is extracted using OIM Analysis software manufactured by TSL Solutions. From the above, the area ratio of the crystal grains having an angle ⁇ formed by the thickness direction (ND) of the titanium alloy plate and the c-axis of the ⁇ phase of 40 ° or less is calculated.
- EBSD electron backscatter diffraction
- the peak of the degree of accumulation of crystal grains is the normal of the plate surface. It is preferable to have an texture that exists within 30 ° from the direction (TD) and has a maximum degree of integration of 4.0 or more. As a result, the c-axis of the crystal grains can be sufficiently integrated in the portion close to the thickness direction (ND) of the titanium alloy plate, and when the titanium alloy plate is used for the copper foil manufacturing drum, the difference in crystal orientation becomes large. The occurrence of the resulting pattern is further suppressed.
- the peak of the degree of accumulation of crystal grains tends to be inclined in the direction perpendicular to the final rolling direction (final rolling width direction (TD)). Therefore, when the final rolling direction is clear, the peak of the degree of accumulation of crystal grains is the final from the normal direction (ND) of the plate surface in the (0001) pole diagram from the normal direction (ND) of the plate surface. It may be present within 30 ° in the rolling width direction (TD).
- the (0001) pole diagram is obtained by chemically polishing the observation surface of the sample of the titanium alloy plate and analyzing the crystal orientation using EBSD. For example, as described above, a region of 1 to 2 mm ⁇ 1 to 2 mm can be scanned at intervals (steps) of 1 to 2 ⁇ m to draw a (0001) pole figure. 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 the maximum degree of integration.
- FIG. 1 shows an example of a (0001) pole figure from the normal direction (ND) from the rolled surface of the titanium alloy plate according to the present embodiment.
- the detected pole points are accumulated according to the inclination in the final rolling direction (RD) and the final rolling width direction (TD), and contour lines of the degree of integration are drawn in the (0001) pole figure.
- the portions where the contour lines are highest are the peaks P1 and P2 of the degree of accumulation of crystal grains. Therefore, in the present embodiment, the peaks P1 and P2 of the crystal grains are present within 30 ° from the ND (center), respectively.
- peak P1 a in the figure is within 30 ° (as in P1 in FIG.
- the peak position may deviate slightly from the TD direction, but deviation within 10 ° is allowed, and a is 30 ° or less. It should be within).
- the maximum degree of integration is 4.0 or more. Usually, the maximum degree of accumulation is the degree of accumulation of peaks P1 or P2 of crystal grains.
- the degree of integration is usually at a portion where the c-axis of the hcp structure is tilted by about 35 to 40 ° in the final rolling width direction (TD) with respect to ND.
- a peak texture is formed.
- the crystal orientation is distributed up to a position tilted by 15 to 20 °, so that crystal grains having different crystal orientations may be adjacent to each other, and a macro pattern is likely to occur.
- the preferred maximum degree of integration is 4.0 or higher. As a result, the crystal orientations are sufficiently accumulated, and the difference in crystal orientations between adjacent crystals can be reduced.
- the maximum degree of integration is preferably 4.0 or more, but more preferably 5.0 or more, still more preferably 6.0 or more, for the purpose of further suppressing the occurrence of macro patterns.
- the degree of accumulation of a specific orientation in the pole figure indicates how many times the frequency of existence of crystal grains having that orientation is higher than that of a structure having a completely random orientation distribution (degree of integration 1). ..
- EBSD electron backscatter diffraction
- the cross section obtained by cutting the titanium alloy plate is chemically polished, and a region of 1 to 2 mm ⁇ 1 to 2 mm is measured in a step of 1 to 2 ⁇ m in a step of about 2 to 10 fields of view by the EBSD method.
- the data is calculated by Texture analysis of the pole figure using the spherical harmonic method using OIM Analysis software manufactured by TSL Solutions.
- twins Titanium may undergo twinning deformation during plastic deformation.
- Twin deformation depends on the crystal grain size as well as the chemical composition, and the larger the grain size, the more likely it is to occur. Therefore, the appearance of crystal grain distribution may become uniform due to the formation of twins.
- twins when twinning deformation occurs, the difference in crystal orientation becomes large, and crystal grains having significantly different crystal orientations are adjacent to each other, and the abrasiveness changes at the boundary, and the crystal is recognized as a pattern. Therefore, it is preferable to suppress twins as much as possible.
- the titanium alloy plate according to the present embodiment has twin grain boundaries with respect to the total grain boundary length of the plate thickness cross section at a position of 1/4 of the plate thickness from the surface when observing the cross section in the plate thickness direction.
- the length ratio is preferably 5.0% or less.
- the ratio of the twin grain boundary length to the total grain boundary length is more preferably 3.0% or less, still more preferably 1.0% or less.
- the lower limit of the above ratio may be 0%, but it is difficult to completely eliminate twins because twins are inevitably deformed by processing such as straightening of a titanium alloy plate. In order to reduce twins, it is important to reduce the amount of correction. For example, it is effective to make the finished plate shape as flat as possible.
- the total grain boundary length and the twin grain boundary length of the plate thickness cross section can be obtained as follows. First, the observed cross section (thickness direction cross section) of the sample of the titanium alloy plate is chemically polished, and the crystal orientation is analyzed using the electron backscatter diffraction method. A region of 1 to 2 mm x 1 to 2 mm is scanned at intervals of 1 to 2 ⁇ m at a position 1/4 of the plate thickness from the surface of the titanium alloy plate of the sample, and a reverse pole map is used using OIM Analysis software manufactured by TSL Solutions. Create (IPF: analyze polyfigure).
- the rotation axis and crystal orientation (rotation angle) of (10-12) twins, (10-11) twins, (11-21) twins, and (11-22) twins generated in titanium Within 2 ° from the theoretical value is regarded as the twin interface (for example, in the case of (10-12) twin, the theoretical values of the rotation axis and the crystal orientation difference (rotation angle) are ⁇ 11-20> and 85 °, respectively). .. Then, the grain boundary having a crystal orientation difference (rotation angle) of 2 ° or more is defined as the total grain boundary length, and the ratio of the twin grain boundary length to the total crystal grain boundary length is calculated. The twin grain boundaries are observed at a position of 1/4 of the plate thickness from the surface because the position can sufficiently represent the structure of the titanium alloy plate. Further, the surface of the titanium alloy plate may not be able to sufficiently represent the structure due to polishing or the like.
- the surface hardness (Vickers hardness) of the surface of the titanium alloy plate to be the drum surface is not particularly limited, but is preferably HV110 or higher. As a result, when a drum is manufactured using a titanium alloy plate and the surface is polished, uniform polishing becomes possible, and macro patterns can be further suppressed.
- the surface hardness (Vickers hardness) of the titanium alloy plate is more preferably HV112 or higher, and even more preferably HV115 or higher.
- the upper limit of the surface hardness (Vickers hardness) of the surface of the titanium alloy plate to be the drum surface is not particularly limited, but if the surface hardness exceeds HV350, the number of polishings increases and it takes time. , Drum productivity is reduced.
- the HV is preferably 350 HV or less. It is more preferably 300 HV or less, still more preferably 250 HV or less. Further, when the amount of processing required for straightening the titanium alloy plate is sufficiently reduced, the HV is preferably 160 or less. It is more preferably HV155 or less, still more preferably HV150 or less.
- the surface hardness of the titanium alloy plate is measured at 3 to 5 points with a load of 1 kg using a Vickers hardness tester in accordance with JIS Z 2244: 2009 after polishing the surface of the titanium alloy plate to a mirror surface, and the average thereof. Can be a value.
- the thickness of the titanium alloy plate according to the present embodiment is not particularly limited, and can be appropriately set according to the application, specifications, and the like of the drum to be manufactured. When used as a material for a copper foil manufacturing drum, the plate thickness decreases with the use of the copper foil manufacturing drum. Therefore, the thickness of the titanium alloy plate is preferably 4.0 mm or more, even if it is 6.0 mm or more. Good.
- the upper limit of the thickness of the titanium alloy plate is not particularly limited, but is, for example, 15.0 mm.
- the chemical composition of the titanium alloy plate is set so as to suppress grain growth and reduce deformation after hot rolling, and the crystals are not only fine but also predetermined.
- a crystal having a uniform size that fits within the standard deviation, and has an ⁇ phase whose crystal structure is a hexagonal close-packed structure, and the angle formed by the ⁇ phase in the [0001] direction with respect to the plate thickness direction is 0 ° or more and 40 ° or less.
- the grain area ratio is 70% or more. Therefore, it is possible to sufficiently suppress the occurrence of macro patterns when used in a drum for producing copper foil.
- the titanium alloy plate according to the present embodiment contains Al of more than 1.8% and 7.0% or less, the Young's modulus of the titanium alloy plate is improved. As a result, in the production of the copper foil production drum, the shrinkage fit of the titanium alloy plate onto the surface of the core material is improved, and the productivity of the copper foil production drum is improved.
- FIG. 2 shows a photograph of a macro pattern on the surface of a titanium alloy plate as an example.
- the “macro pattern” refers to a pattern in which parts having different colors occur in a streak shape with a length of several mm parallel to the rolling direction (for reference, the macro pattern in FIG. 3 and FIG. 2).
- the figure that emphasizes the macro pattern is shown so that the position of can be seen).
- the surface of the titanium alloy plate is made of # 800 emery paper. The surface can be evaluated by observing the surface with a solution of 10% nitric acid and 5% hydrofluoric acid.
- the titanium alloy plate according to the present embodiment can sufficiently suppress the occurrence of macro patterns when used in a drum for producing copper foil, and is suitable as a material for a drum for producing copper foil.
- the copper foil manufacturing drum 20 according to the present embodiment is a part of the electrodeposition drum, and is a cylindrical inner drum 21 and a titanium alloy plate adhered to the outer peripheral surface of the inner drum 21.
- the titanium alloy plate 22 has a 22 and a welded portion 23 provided at a butt portion of the titanium alloy plate 22, and the titanium alloy plate 22 is the titanium alloy plate according to the present embodiment described above.
- the copper foil manufacturing drum 20 according to the present embodiment is a copper foil manufacturing drum manufactured by using the titanium alloy plate according to the present embodiment. Since the copper foil manufacturing drum 20 according to the present embodiment uses the titanium alloy plate according to the present embodiment on the surface of the drum on which the copper foil is deposited, the occurrence of macro patterns is suppressed and a high quality copper foil is produced. Can be manufactured.
- the size of the copper foil manufacturing drum according to the present embodiment is not particularly limited, but the diameter of the drum is, for example, 1 to 5 m.
- the inner drum 21 may be a known one, and the material thereof may not be a titanium alloy plate, for example, mild steel or stainless steel.
- the titanium alloy plate 22 is wound around the outer peripheral surface of the cylindrical inner drum 21, and the butt portion is welded to the inner drum 21. Therefore, the welded portion 23 exists in the butt portion.
- the metal structure has an ⁇ phase of 98.0% or more in volume fraction, and the particle size number conforms to JIS G 0551: 2013, which is 6 or more and 11 or less. Is.
- the particle size number is preferably 7 or more and 10 or less.
- the particle size number of the crystal grain of the metal structure of the welded portion can be measured by a comparative method, a counting method and a cutting method according to JIS G 0551: 2013.
- the welded portion 23 of the copper foil manufacturing drum 20 has, for example, the following metal structure.
- the metallographic structure of the weld is mainly ⁇ phase, that is, mainly contains ⁇ phase.
- the ⁇ phase corrodes in preference to the ⁇ phase. Therefore, from the viewpoint of achieving uniform corrosion and suppressing the generation of macro patterns, it is preferable that the ⁇ phase is small.
- the volume fraction of the ⁇ phase of the metal structure of the welded portion is 2.0% or less.
- the rest of the metal structure of the titanium alloy plate is the ⁇ phase.
- the volume fraction of the ⁇ phase is preferably 1.0% or less, and more preferably the texture of the welded portion is ⁇ single phase.
- the volume fraction of the ⁇ phase in the metal structure of the welded portion according to the present embodiment is preferably 98.0% or more, more preferably 99.0% or more, and further preferably 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 metal portion.
- the difference in hardness (Vickers hardness) between the welded portion and the drum base material is preferably ⁇ 25 or less. More preferably, it is ⁇ 15 or less.
- the hardness of the welded portion is, for example, HV110 or higher, more preferably HV112 or higher, and even more preferably HV115 or higher.
- the hardness of the welded part is measured at 3 to 5 points with a load of 1 kg using a Vickers hardness tester in accordance with JIS Z 2244: 2009 after polishing the surface of the welded part until it becomes a mirror surface, and the average value is used. be able to.
- the difference between the crystal grain size of the formed weld and the crystal grain size of the titanium alloy plate is preferably -1.0 or more and 1.0 or less.
- the titanium alloy plate according to the present embodiment described above may be produced by any method, and for example, it can be produced by the method for producing a titanium alloy plate according to the present embodiment described below.
- a preferred method for producing a titanium alloy plate according to this embodiment is (I) A first step (heating step) of heating a titanium alloy having the above-mentioned chemical composition to a temperature of 750 ° C. or higher and 950 ° C. or lower. (II) A second step (rolling step) of rolling to obtain a titanium alloy plate after the heating step, (III) The third step (annealing step) of annealing the titanium alloy after the rolling step and Have.
- each step will be described.
- the material of the titanium alloy plate is prepared prior to each of the above-mentioned steps.
- the material those having the above-mentioned chemical composition can be used, and those produced by a known method can be used.
- an ingot is produced from titanium sponge by various melting methods such as a vacuum arc remelting method, an electron beam melting method, or a hearth melting method such as a plasma melting method.
- a material can be obtained by hot forging or rolling the obtained ingot at a temperature in the ⁇ -phase high temperature region or the ⁇ -phase single-phase region.
- the material may be subjected to pretreatment such as cleaning treatment and cutting, if necessary.
- a rectangular slab shape that can be hot-rolled is manufactured by the hearth melting method, it can be directly subjected to the following first step and second step (heating, hot rolling) without hot forging or the like. Good.
- This step is a heating step performed prior to hot rolling of the titanium material.
- the material of the titanium alloy plate is heated to a temperature of 750 ° C. or higher and 950 ° C. or lower.
- the heating temperature is 750 ° C. or higher, it is possible to prevent the titanium alloy plate from cracking in the hot rolling in the second step.
- the heating temperature is 950 ° C. or lower, it is possible to prevent the formation of a texture (T-texture) in which the c-axis of the hcp structure is oriented in the plate width direction in the hot rolling in the second step.
- the heating temperature is less than 750 ° C., for example, when coarse particles are generated in hot forging, casting, etc., the titanium alloy plate is cracked from the coarse particles in the hot rolling in the second step. May occur.
- the heating temperature exceeds 950 ° C.
- a coarse texture (T-texture) in which the c-axis of the hcp structure is oriented in the plate width direction is generated in the hot rolling in the second step.
- the heating temperature is 950 ° C. or lower.
- the heating temperature is preferably ⁇ -transformation point or lower, more preferably 900 ° C.
- the heating temperature is preferably 900 ° C. or lower, and particularly when the Al content is 3.0% or less, the heating temperature is preferably 880 ° C. or lower.
- the " ⁇ transformation point” means the boundary temperature at which the ⁇ phase begins to be generated when the titanium alloy is cooled from the ⁇ phase single phase region.
- the ⁇ transformation point can be obtained from the phase diagram.
- the phase diagram can be obtained by, for example, the CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) method.
- the phase diagram of the titanium alloy is obtained by the CALPHAD method using Thermo-Calc, which is an integrated thermodynamic calculation system of Thermo-Calc Waterare AB, and a predetermined database (TI3), and the ⁇ transformation point is determined. Can be calculated.
- the material of the heated titanium alloy plate is rolled (hot rolling). Then, in this step, the total reduction rate may be 80% or more, and the ratio of the rolling reduction rate at 200 ° C. or higher and 650 ° C. or lower to the total reduction rate may be 5% or more and 70% or less. preferable. As a result, the crystal grains are uniformly miniaturized as described above, and an aggregate structure in which 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 above heating temperature. When the total reduction rate is 80% or more, the coarse particles generated in hot forging, casting, etc. can be sufficiently finely divided, and T-texture can be prevented from occurring.
- the total reduction rate is less than 80%, the structure generated in hot forging, casting, etc. may remain, and coarse grains may be formed or T-texture may occur.
- a macro pattern is generated in the produced drum.
- the total reduction rate in this step is preferably 85% or more.
- the higher the reduction rate the better the structure, so it may be determined according to the required product size and the characteristics of the manufacturing mill.
- the ratio of the rolling reduction rate of the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower to the total reduction rate is 5% or more and 70% or less. Is preferable. Especially when the Al content is low (for example, 3.0% or less), it is preferable to satisfy the above.
- the ratio of the rolling reduction rate of the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower is less than 5% of the total reduction rate, such as when the total rolling is performed at more than 650 ° C., the reduction amount in this temperature range. Is insufficient, recovery occurs during subsequent cooling, and a portion with a small amount of strain occurs.
- the heat treatment after hot spreading increases the variation in crystal grain size. Variations in crystal grain size are likely to occur especially when the Al content that suppresses crystal grain growth is small.
- the crystal structure includes the ⁇ phase which is a hexagonal close-packed structure, and the plate thickness. In a structure in which the angle formed by the ⁇ phase in the [0001] direction with respect to the direction is 0 ° or more and 40 ° or less and the area ratio of the crystal grains is 70% or more, and / or in the (0001) pole view from the normal direction of the plate surface.
- the plate shape is not good. It will be stable. In this case, the amount of processing in the subsequent straightening becomes large, strain is introduced, the difference in the amount of strain becomes large between the straightened portion and the other portion, and the variation in crystal grain size becomes large in the subsequent heat treatment.
- the ratio of the rolling reduction of the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower to the total reduction ratio is preferably 10% or more, more preferably 15% or more.
- the ratio of the rolling reduction rate of the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower exceeds 70% of the total rolling reduction rate, such as when the total rolling is performed at 650 ° C. or lower, the plate shape is not good. It will be stable. In this case, the amount of processing in the subsequent straightening becomes large, strain is introduced, the difference in the amount of strain becomes large between the straightened portion and the other portion, and the variation in crystal grain size becomes large in the subsequent heat treatment. Furthermore, if correction is performed after heat treatment, strain affects and only that portion is likely to be corroded, which may cause a macro pattern. Therefore, the ratio of the rolling reduction rate of the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower is preferably 70% or less of the total reduction rate. It is more preferably 65% or less, still more preferably 60% or less.
- the surface temperature of the titanium alloy plate at the completion of hot rolling in this step is preferably 200 ° C. or higher.
- the surface temperature of the titanium alloy plate at the completion of hot rolling is preferably 300 ° C. or higher.
- the rolling may be unidirectional rolling in which the titanium alloy plate is stretched in the longitudinal direction, but in addition to rolling in the longitudinal direction, rolling may be performed in a direction orthogonal to the longitudinal direction. Good.
- the degree of integration of the texture can be further increased in the obtained titanium alloy plate.
- the rolling reduction rate in the final rolling direction is L (%) and the rolling reduction rate in the direction orthogonal to the final rolling direction is T (%)
- the L / T is 1.0. It is preferably 10.0 or less.
- the L / T is more preferably 1.0 or more and 5.0 or less.
- the titanium alloy plate when rolling at 200 ° C. or higher and 650 ° C. or lower, the titanium alloy plate may be held for a certain period of time and waited for cooling.
- the strain generated in rolling is prevented from being released by reheating, and the strain can be stably applied to the titanium alloy plate.
- the degree of integration of the texture of the titanium alloy plate can be increased, and partial abnormal grain growth during the heat treatment described later can be suppressed.
- cold rolling may be performed.
- the cold rolling is rolling at a temperature of 200 ° C. or lower, and may be performed by unidirectional rolling or cross rolling.
- the reduction rate is preferably 10% or more. By setting the reduction ratio to 10% or more, strain can be introduced uniformly, and variations in crystal grain size that may occur in the subsequent heat treatment can be reduced.
- the oxide scale on the surface of the titanium alloy plate after hot rolling is removed in advance.
- the oxidation scale may be removed by, for example, shot blasting, pickling following shot blasting, or machining such as cutting.
- Annealing may be performed at a temperature below the ⁇ transformation point, if necessary, prior to removal of the oxide scale. Such annealing is preferably performed at ( ⁇ transformation point-50) ° C.
- the Al content of the titanium alloy plate in the case of cold rolling is preferably 3.5% or less. Further, when the ratio of the twin grain boundary length to the total grain boundary length is reduced, it is preferable not to perform cold rolling.
- the titanium alloy plate is heat-treated (annealed) at a temperature of 600 ° C. or higher and ⁇ transformation point ° C. or lower for 20 minutes or longer.
- the unrecrystallized grains can be precipitated as fine recrystallized grains, and the crystals in the metal structure of the obtained titanium alloy plate can be made uniform and fine.
- the occurrence of macro patterns can be suppressed more reliably.
- the annealing temperature is preferably 650 ° C. or higher. From the viewpoint of suppressing coarsening of crystal grains, it is preferable to set the annealing temperature to ⁇ transformation point or lower. More preferably, it is 800 ° C. or lower.
- the upper limit of the annealing time is not particularly limited, but is, for example, 5 hours or less. In particular, when the Al content having the effect of suppressing crystal grain growth is small, the annealing time is preferably 90 minutes or less from the viewpoint of suppressing coarsening of crystal grains.
- the heat treatment may be performed in an atmospheric atmosphere, an inert atmosphere or a vacuum atmosphere.
- the oxide scale is removed.
- the removal of the oxide scale is not particularly limited, and may be performed by, for example, shot blasting, pickling following shot blasting, or machining such as polishing or cutting.
- shot blasting may cause strain to be introduced into the titanium alloy plate, so it is better to avoid removing the oxide scale by shot blasting.
- the annealing method is not particularly limited, and may be a continuous heating method or a batch heating method.
- Examples of the post-treatment include removal of oxide scale and the like by pickling and cutting, cleaning treatment, and the like, which can be appropriately applied as needed.
- a straightening process of the titanium alloy plate may be performed.
- the straightening process can be performed by, for example, vacuum creep straightening (VCF; Vacuum creep fratting). The method for manufacturing the titanium alloy plate according to the present embodiment has been described above.
- a method for manufacturing a copper foil manufacturing drum according to the present embodiment is a titanium wire for welding (titanium for welding according to the present embodiment) in which two adjacent ends of the titanium alloy plate according to the present embodiment processed into a cylindrical shape are described later. It has a process (welding process) of welding using a wire rod).
- the processing of the titanium alloy plate into a cylindrical shape, welding conditions, and the like can be performed by known methods.
- two adjacent ends of a titanium alloy plate processed into a cylindrical shape are built-up welded using the titanium wire for welding described above to form a welded portion (build-up welded portion).
- the welded portion is processed cold or warm, it is preferable to pre-fill the built-up portion.
- the thickness of the pre-filling can be, for example, 10 to 50% of the thickness of the titanium alloy plate.
- the build-up welded portion may be pressed cold or warm at 200 ° C. or lower.
- the reduction ratio is preferably 10% or more and 50% or less in order to prevent the generation of straw due to a high processing rate and to ensure that the solidified structure has a uniform fine equiaxed structure.
- heat treatment annealing may be performed after welding.
- the heat treatment can be performed, for example, at a temperature of 500 ° C. or higher and 850 ° C. or lower for 1 minute or longer and 10 minutes or shorter. By performing the heat treatment at 850 ° C. or lower for 10 minutes or less, it is possible to prevent coarsening of crystal grains and coarsening of some of the crystal grains, and a uniform fine crystal structure can be obtained.
- the titanium wire for welding according to the present embodiment can be used for manufacturing a titanium drum for producing copper foil, and more specifically, for welding adjacent ends of a titanium alloy plate bent into a cylindrical shape. Used for.
- the titanium wire for welding according to this embodiment is based on mass%.
- the balance preferably has a chemical composition containing Ti and impurities.
- the content of one or more selected from the group consisting of Sn, Zr and Al is 0.2% by mass or more and 6.0% by mass or less in total.
- the metal structure of the obtained welded portion can be mainly composed of the ⁇ phase, and the formation of the ⁇ phase can be suppressed, so that the corrosion resistance of the welded portion can be improved.
- the crystal grains in the metal structure of the obtained welded portion can be made sufficiently fine, and the generation of macro patterns caused by the crystal grains can be suppressed.
- the content of one or more selected from the group consisting of Sn, Zr and Al is less than 0.2% by mass in total, coarse particles are formed in the crystal grains in the metal structure of the obtained welded portion. May occur, and the occurrence of macro patterns cannot be suppressed.
- the content of one or more 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.
- the content of one or more selected from the group consisting of Sn, Zr and Al exceeds 6.0% by mass in total, it is obtained due to the adverse effect caused by the excessive content of Sn, Zr and Al described above.
- the occurrence of macro patterns cannot be suppressed in the welded parts.
- the content of one or more selected from the group consisting of Sn, Zr and Al is preferably 5.5% by mass or less in total, and more preferably 5.0% by mass or less in total.
- Sn is a neutral element, and is an element capable of suppressing the growth of crystal grains in the welded portion by being contained in the titanium wire for welding.
- the Sn content is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more.
- the Sn content is preferably 6.0% by mass or less, and more preferably 5.5% by mass or less.
- the Zr is also a neutral element, and is an element that can suppress the growth of crystal grains by being contained in the titanium wire for welding.
- the Zr content is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more.
- the Zr content is preferably 5.5% by mass or less, and more preferably 5.0% by mass or less.
- Al is an ⁇ -stabilizing element, and like Sn and Zr, it can suppress the growth of crystal grains by being contained in the titanium wire for welding, and the titanium wire for welding and the welding formed by using the same. Contributes to improving the strength of the part.
- the Al content is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more.
- 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 of the solidified structure (welded portion) of the titanium wire for welding before heat treatment, resulting in processing cracks.
- the Al content is preferably 5.0% by mass or less, more preferably 4.5% by mass or less.
- Al is an element that can contribute to the improvement of the strength of the welded portion, and increases the hardness of the welded portion. Therefore, when suppressing the increase in hardness of the welded portion, it is preferable to include it together with Sn and / or Zr.
- the total content of Sn and Al is 0.2% by mass or more and 6.0% by mass or less, preferably 0.3% by mass or more and 5.5% by mass or less.
- the total content of Zr and Al is 0.2% by mass or more and 6.0% by mass or less, preferably 0.3% by mass or more and 5.5% by mass or less.
- the above-mentioned Sn, Zr and Al may be contained in the above-mentioned amounts in total, and one or two of them may not be contained in the titanium wire for welding.
- the O content is an ⁇ -stabilizing element, and can improve the strength at room temperature while suppressing an increase in high-temperature strength, and can improve the hardness of the welded portion.
- the O content is 0.01% by mass or more. From the viewpoint of controlling the hardness of the welded portion, the O content is preferably 0.015% by mass or more, more preferably 0.02% by mass or more. On the other hand, if the O content exceeds 0.70% by mass, cracks will occur in the build-up process during welding. Therefore, the O content is 0.70% by mass or less.
- the O content is preferably 0.60% by mass or less, more preferably 0.50% by mass or less.
- At least a part of O is present in the titanium wire for welding as an oxide of granular Ti, Sn, Zr and / or Al, for example, as TIO 2 , SnO, SnO 2 , ZrO 2 , Al 2 O 3 . It is preferable to do so.
- These oxides are dissociated by an arc at the time of welding, and the dissociated O forms an oxide film at the welded portion, suppresses local contact with the arc, and stabilizes the welded portion to homogenize the welded portion. As a result, the build-up shape and workability can be improved during welding. O is considered to dissolve uniformly in the drum weld.
- the peak intensities of ⁇ -titanium obtained by the X-ray diffraction method for the titanium wire for welding are A, TiO 2 (110), ZrO 2 (111), SnO 2 (110) and Al 2 O 3 (
- the B / A line intensity ratio
- the B / A is more preferably 0.015 or more and 0.10 or less, and further preferably 0.02 or more and 0.09 or less.
- the X-ray diffraction of the titanium wire for welding according to the present embodiment is carried out for a cross section perpendicular to the longitudinal direction using a Cu tube in a current of 40 mA, a voltage of 40 kV, and a range of 10 to 110 ° of 2 ⁇ .
- the measurement is carried out at intervals of 0.01 ° at 1 s / point, and can be performed by rotating the sample 360 ° at each measurement point.
- Fe is an element that reinforces the ⁇ phase. If the amount of ⁇ -phase precipitated in the welded portion increases, it affects the formation of macro patterns. Therefore, the upper limit of the Fe content in the titanium wire for welding is set to 0.500%.
- the Fe content is preferably 0.100% or less, more preferably 0.080% or less.
- N, C, and H are elements that reduce ductility and processability when contained in large amounts. 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.
- N, C, and H are impurities, and the lower the content thereof, the more preferable. However, these elements may be mixed in during 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 balance 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.
- the impurities include Cl, Na, Mg, Si, Ca mixed in the refining step and Cu, Mo, Nb, Ta, V mixed in from scrap.
- the content thereof is, for example, 0.10% by mass or less, and if the total amount is further 0.50% by mass or less, there is no problem.
- the wire diameter of the titanium wire for welding according to the present embodiment is not particularly limited, and is, for example, 0.8 mm or more and 3.4 mm or less.
- the cross-sectional shape 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 be any shape.
- Titanium wire for welding can be manufactured by cold, warm and hot plastic working such as hole die wire drawing, roll die wire drawing, caliber rolling, etc., and powder metallurgy.
- the structure of the welded portion is mainly composed of ⁇ phase, and crystals are formed.
- the grains can be refined.
- the hardness of the welded portion can be controlled by containing an appropriate amount of O in the titanium wire for welding.
- a titanium wire for welding can be produced by a method of crimping an oxide to the surface, a method of adhering an oxide to the surface of a rod, vacuum annealing at 750 to 1000 ° C., and diffusion bonding.
- a method of manufacturing a titanium wire for welding by inserting a powdery oxide into a hollow titanium pipe, but the distribution of the oxide tends to vary, and in that case, it contributes to the composition fluctuation in the welded part. The hardness and crystal grain size of the same part will fluctuate. Therefore, in the present embodiment, the method of inserting the powdery oxide into the titanium tube is not adopted and is excluded from the target.
- ratio of rolling reduction rate of 200 to 650 ° C refers to the ratio of rolling reduction rate of titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower to the total rolling reduction ratio, and is “rolling ratio (L / T)”.
- Rolling ratio Shows the value of L / T when the rolling reduction ratio in the final rolling direction is L (%) and the rolling reduction ratio in the direction orthogonal to the final rolling direction is T (%).
- hot rolling is temporarily stopped in order to roll the titanium alloy plate at 200 ° C. or higher and 650 ° C. or lower, except for Comparative Example 1. After waiting for cooling to 650 ° C. or lower, hot rolling was restarted. For some examples, pre-annealing and cold rolling were performed.
- the average crystal grain size D and the standard deviation of the grain size distribution of the crystals of the metal structure of the titanium alloy plate according to each invention example and comparative example were measured and calculated as follows.
- the cross section of the cut titanium alloy plate was measured in 10 fields in 2 ⁇ m steps in a region of 2 mm ⁇ 2 mm using chemical abrasive paper and electron backscatter diffraction method.
- the standard deviation ⁇ in the lognormal distribution was calculated from the crystal grain size distribution.
- the area ratio of crystal grains whose angle ⁇ between the thickness direction (ND) of the titanium alloy plate and the [0001] direction (c-axis) of the ⁇ phase is 40 ° or less was calculated by the following method. ..
- the cross section of the titanium alloy plate is chemically polished and crystal orientation analysis is performed using EBSD.
- a region of 2 mm ⁇ 2 mm was measured in 10 fields of view in steps 2 ⁇ m for each of the lower surface of the titanium alloy plate and the central portion of the plate thickness.
- measurement point data in which the angle between the ND and the c-axis is 40 ° or less was extracted using OIM Analysis software manufactured by TSL Solutions.
- Al segregation The presence or absence of Al segregation (Al uniformity) was confirmed as follows.
- the beam diameter is set to 500 ⁇ m
- the step size is set to 500 ⁇ m, which is the same as the beam diameter
- composition analysis is performed for a region of 20 mm ⁇ 20 mm or more on the surface perpendicular to the plate thickness direction at a position 1/4 of the plate thickness from the surface of the titanium alloy plate. went.
- JIS Class 1 industrial pure titanium and the target titanium alloy plate were analyzed, and a calibration curve obtained by linear approximation from the result was used.
- the area ratio of the region where the concentration of Al was ([Al%] ⁇ 0.2) mass% or more ([Al%] +0.2) mass% or less was determined.
- the surface of the titanium alloy plate according to each invention example and comparative example of 50 ⁇ 100 mm size of about 5 to 10 sheets is polished with # 800 emery paper, and 10% nitric acid and hydrofluoric acid are used. Observation was performed by corroding the surface with a 5% solution. Next, a streak-like pattern having a length of 3 mm or more was used as a macro pattern, and the evaluation was performed as follows according to the average generation rate.
- Occurrence rate is 1.0 pieces / sheet or less (very good, 1.0 pieces or less in 50 x 100 mm)
- Occurrence rate exceeds 10.0 pieces / sheet (failure, more than 10.0 pieces in 50 x 100 mm)
- polishing property The polishing was performed with the above-mentioned # 800 emery paper for observing the macro pattern, with the polishing time set to 1 minute. If the surface skin is removed in 1 minute, the productivity of drum production is judged to be maintained, and the polishability is good (OK). If the surface skin is not removed in 1 minute, the drum production is performed. It was judged to be unfavorable (NG) because it was judged that the productivity would be reduced.
- the shrink-fitting property was evaluated as follows.
- the shrink fit is affected by Young's modulus and shape ratio (for example, in the case of a pipe plate, the ratio of the outer diameter of the inner pipe to the inner diameter of the outer pipe).
- Young's modulus and shape ratio for example, in the case of a pipe plate, the ratio of the outer diameter of the inner pipe to the inner diameter of the outer pipe.
- Young's modulus the smaller the amount of deformation can be achieved, so that the heating temperature can be lowered and the workability is improved. Therefore, when the Young's modulus is 135 GPa or more, the shrink fit is excellent.
- the obtained analysis results and evaluation results are shown in Tables 5 and 6.
- the "area ratio (%) of crystal grains having an angle ⁇ of 0 ° or more and 40 ° or less" shown in Tables 5 and 6 is a crystal in which the angle formed by the c-axis of the ⁇ phase with respect to the plate thickness direction is 0 ° or more and 40 ° or less. It is the area ratio of grains.
- the “Al uniformity (%)” shown in Table 2 is the area of the region where the concentration of Al is ([Al%] ⁇ 0.2) mass% or more ([Al%] +0.2) mass% or less. The rate.
- "RT" in the "cold rolling process” shown in Table 2 means room temperature.
- Example 2 Assuming application to a copper foil manufacturing drum, a titanium alloy plate obtained by the same method as the invention example of Example 1 shown in Table 7 is used as a base material, processed into a cylindrical shape having a diameter of 1 m, and then butt-welded. The portions (two adjacent ends) were welded using the titanium wire for welding shown in Table 7. For welding, the pre-filling thickness was set to 25% or less of the plate thickness of the base metal. Then, after the pre-filling, only the pre-filled portion was reduced to the base metal thickness at a temperature of 200 ° C. or lower. Finally, the welded portion was heat-treated at 600 to 800 ° C. for 20 to 90 minutes to obtain a welded sample of the titanium wire for welding according to each invention example and each comparative example.
- the crystal grain size in the metal structure of the obtained welded portion was measured according to JIS G 0551: 2013 according to a comparative method, and obtained as a particle size number (GSN). Further, the concentration distribution of Fe or ⁇ phase stabilizing element is measured with respect to the metal structure of the welded portion using SEM / EPMA, and the concentration of Fe or the total concentration of ⁇ phase stabilizing element is the average concentration in the measurement range. The point (concentrated part) higher than 1 mass% was defined as the ⁇ phase, and the area ratio was calculated.
- the obtained area fraction is the volume fraction of the ⁇ phase
- the area fraction of the portion where the ⁇ phase stabilizing element is not concentrated (other than the concentrated portion) is the volume fraction of the ⁇ phase.
- the volume fraction of the phase was determined. Further, the Vickers hardness (Hv) of the welded portion and the base metal in the welded samples according to each of the obtained invention examples and comparative examples was measured at 3 to 5 points under a load of 1 kg, and calculated from the average value.
- the step ( ⁇ m) at the boundary between the welded portion and the base metal portion was measured at ⁇ c: 0.8 mm, ⁇ s: 2.5 ⁇ m, and rtip: 2 ⁇ m according to JISB0633: 2001.
- the surface of each titanium alloy plate of 50 ⁇ 100 mm size of about 5 to 10 sheets was polished with a # 800 buff, and a solution of 10% nitric acid and 5% hydrofluoric acid was prepared. The surface was observed after corrosion using.
- a streak-like pattern generated with a length of 3 mm or more was made into a macro pattern, and the evaluation was performed as follows according to the average of the generation rate.
- Occurrence rate is 1.0 pieces / sheet or less (very good, 1.0 pieces or less in 50 x 100 mm)
- Occurrence rate exceeds 10.0 pieces / sheet (failure, more than 10.0 pieces in 50 x 100 mm)
- the present invention it is possible to provide a titanium alloy plate capable of suppressing the generation of macro patterns when used as a drum for producing copper foil, and a copper foil production drum manufactured using the titanium alloy plate. It becomes.
- Electrode plate 40 Winding part 50 Guide roll 60 Winding roll A Copper foil 20 Copper foil manufacturing drum 21 Inner drum 22 Titanium alloy plate 23 Welded part
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Abstract
Description
本願は、2019年04月17日に、日本に出願された特願2019-078824号、及び、2019年04月17日に、日本に出願された特願2019-078828号に基づき優先権を主張し、その内容をここに援用する。
しかしながら、特許文献1~6の技術では、芯材とチタン板との焼き嵌め作業に手間を要し、銅箔製造ドラムの生産性について改善の余地があった。
銅箔製造ドラムの表面における溶接部の割合は大きくないものの、近年、溶接部のマクロ模様の低減に対する要求が高まっている。
また、本発明の好ましい目的は、銅箔製造用のドラムに使用した際にマクロ模様の発生を抑制可能であり、かつ焼き嵌め性に優れたチタン合金板及び同チタン合金板を用いて製造される銅箔製造ドラムを提供することにある。
本発明者らは、この知見に基づき、チタン合金板の硬さ、結晶粒サイズ、結晶方位、第二相、及び元素の分布に着目して検討を行った。その結果、Alを一般の銅箔製造用のドラムに用いられるチタン合金板よりも多量に含有させると、粒成長が抑制されて微細組織を形成しやすくなり、チタン合金板の硬度が大きくなり、かつ、チタン合金板のヤング率が向上することを見出した。
[1]本発明の一態様に係るチタン合金板は、質量%で、Sn:0%以上2.0%以下、Zr:0%以上5.0%以下、及びAl:0%以上7.0%以下、からなる群より構成される1種又は2種以上:合計で0.2%以上7.0%以下、N:0.100%以下、C:0.080%以下、H:0.015%以下、O:0.700%以下、及び、Fe:0.500%以下、を含有し、残部がTi及び不純物を含有する化学組成を有し、平均結晶粒径が40μm以下であり、単位μmでの結晶粒径の対数に基づく粒径分布の標準偏差が0.80以下であり、結晶構造が六方最密充填構造であるα相を含み、板厚方向に対する前記α相の[0001]方向のなす角が0°以上40°以下の結晶粒の面積率が70%以上である。
[2]上記[1]に記載のチタン合金板は、板面の法線方向からの(0001)極点図において、電子線後方散乱回折法の球面調和関数法を用いた極点図の展開指数を16、ガウス半値幅を5°としたときのTexture解析により算出される集積度のピークが、前記板面の前記法線方向から30°以内に存在し、かつ、最大集積度が4.0以上である集合組織を有してもよい。
[3]上記[1]または[2]に記載のチタン合金板は、前記平均結晶粒径を単位μmでDとした際に、前記粒径分布の標準偏差が、(0.35×lnD-0.42)以下であってもよい。
[4]上記[1]~[3]のいずれかに記載のチタン合金板は、板厚方向断面を観察した際に、表面から板厚1/4の位置における板厚断面の全結晶粒界長さに対する双晶粒界長さの割合が、5.0%以下であってもよい。
[5]上記[1]~[4]のいずれかに記載のチタン合金板は、前記化学組成において、Sn:0.2%以上2.0%以下、Zr:0.2%以上5.0%以下、及びAl:0.2%以上3.0%以下、からなる群より構成される1種又は2種以上を、合計で0.2%以上5.0%以下含有してもよい。
[6]上記[1]~[4]のいずれかに記載のチタン合金板は、前記化学組成において、Al:1.8%超7.0%以下を含有し、ビッカース硬さが350Hv以下であってもよい。
[7]上記[6]に記載のチタン合金板は、質量%での、Al含有量を[Al%]、Zr含有量を[Zr%]、Sn含有量を[Sn%]、O含有量を[O%]としたとき、下記式(1)で示されるAl当量Aleqが、7.0以下であってもよい。
Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] 式(1)
[8]上記[6]または[7]に記載のチタン合金板は、電子線マイクロアナライザを用いて、表面から板厚1/4の位置における板厚方向に垂直な面20mm×20mm以上の分析領域を組成分析したときに、Alの平均含有量を[Al%]として、前記分析領域の面積に対する、Alの濃度が([Al%]-0.2)質量%以上([Al%]+0.2)質量%以下である領域の面積率が90%以上であってもよい。
[9]上記[1]~[8]のいずれかに記載のチタン合金板は、前記α相を98.0体積%以上含有してもよい。
[10]上記[1]~[9]のいずれかに記載のチタン合金板は、銅箔製造ドラム用チタン合金板であってもよい。
[11]本発明の別の態様に係る銅箔製造ドラムは、円筒状のインナードラムと、前記インナードラムの外周面に被着された、[1]~[10]のいずれかに記載のチタン合金板と、前記チタン合金板の突合せ部に設けられた溶接部と、を有し、前記溶接部の金属組織が、体積率で、98.0%以上のα相を有し、JIS G 0551:2013に準拠した粒度番号で、6以上11以下である。
[12]本発明の別の態様に係る銅箔製造ドラムの製造方法は、円筒状に加工したチタン合金板の隣接する2つの端部を、溶接用チタン線材を用いて溶接する溶接工程を有し、前記溶接用チタン線材が、質量%で、Sn、ZrおよびAlからなる群から選択される1種以上:合計で0.2%以上6.0%以下、O:0.01%以上0.70%以下、N:0.100%以下、C:0.080%以下、H:0.015%以下、およびFe:0.500%以下、を含み、残部がTiおよび不純物を含む化学組成を有する。
[13]上記[12]に記載の銅箔製造ドラムの製造方法は、前記溶接用チタン線材において、前記Oの少なくとも一部が、Ti、Sn、ZrおよびAlからなる群から選択される1種以上の元素の酸化物として存在していてもよい。
また、本発明の好ましい態様によれば、銅箔製造用のドラムに使用した際にマクロ模様の発生を抑制可能であり、かつ焼き嵌め性に優れるチタン合金板を提供することが可能となる。
また、本発明の好ましい態様によれば、銅箔製造ドラムの溶接部におけるマクロ模様の発生を抑制する、銅箔製造ドラムの製造方法、及び銅箔製造ドラムを提供することが可能となる。
<1.チタン合金板>
まず、本実施形態に係るチタン合金板について説明する。本実施形態に係るチタン合金板は、銅箔製造用のドラム(銅箔製造ドラム)の材料として利用されることを想定している。したがって、本実施形態に係るチタン合金板は、銅箔製造ドラム用チタン合金板であるともいえる。銅箔製造ドラムにおいて使用される場合、チタン合金板の一方の面が、ドラムの円筒表面を構成する。
まず、本実施形態に係るチタン合金板の化学組成を説明する。本実施形態に係るチタン合金板は、質量%で、Sn:0%以上2.0%以下、Zr:0%以上5.0%以下、及びAl:0%以上7.0%以下、からなる群より構成される1種又は2種以上を、合計で0.2%以上7.0%以下、N:0.100%以下、C:0.080%以下、H:0.015%以下、O:0.700%以下、及び、Fe:0.500%以下、を含有し、残部がTi及び不純物を含有する。以下では特に断りのない限り、化学組成に関する「%」の表記は「質量%」を表わすものとする。
各元素の含有量の限定理由について説明する。
Sn、Zr及びAlからなる群から選択される1種又は2種以上の含有量の合計が0.2%以上であれば、安定的に結晶粒成長を抑制することができる。
一方、Sn、Zr及びAlからなる群から選択される1種又は2種以上の含有量の合計を7.0%以下とすることで、上述した、熱間圧延後のチタン合金板の変形が生じない程度の高温強度となる。高温強度の点からは、好ましくは、Al含有量が0.2%以上3.0%以下でかつ、Sn、Zr及びAlからなる群から選択される1種又は2種以上の含有量の合計は、0.5%以上5.0%以下である。Sn、Zr及びAlからなる群から選択される1種又は2種以上の含有量の合計は、より好ましくは0.5%以上4.0%以下である。
また、Snは、チタン中のα相及びβ相に固溶することで、それぞれの相を安定化させる。Sn含有量が多すぎると、高温強度が高くなり、熱間圧延時の反力により、熱間圧延後の板形状が歪み、波形状となりやすい。波形状となったチタン合金板は、形状を矯正するための加工により、ひずみが付与されることで、チタン合金板の結晶に転位が導入される。この転位が原因となり、マクロ模様が発生しやすくなる。また、Sn含有量が多すぎると、チタン合金板の靭性が小さくなり、銅箔製造ドラム製造時の焼き嵌め性が低下し、生産性が低下する。そのため、Sn含有量は、2.0%以下であることが好ましく、より好ましくは1.5%以下である。Snは、チタン合金板において必須ではないことから、Zrおよび/またはAlが合計で0.2%以上含まれている場合には、Sn含有量は0%でもよい。
一方、Zrは、チタン中のα相及びβ相に固溶することで、それぞれの相を安定化させる元素である。Zr含有量が多すぎると、α相及びβ相の2相が熱的に安定して存在する温度範囲が広くなり、加熱時にβ相が析出しやすくなる。β相は、α相よりも優先して腐食するので、β相を含むチタン合金板を表面に有するドラムを銅箔の製造に用いた場合、β相が優先的に腐食されてドラム表面にマクロ模様が生じる。その結果、銅箔にそのマクロ模様が転写される可能性がある。また、凝固偏析により、チタン合金板の部位間に強度差が生じ、得られたチタン合金板を研磨した際にマクロ模様が発生する。そのため、Zr含有量は、5.0%以下である。Zr含有量は、好ましくは、4.5%以下であり、より好ましくは、4.0%である。Zr含有量は、さらに好ましくは、2.5%以下であり、一層好ましくは、2.0%以下である。Zrは、チタン合金板において必須ではないことから、Snおよび/またはAlが合計で0.2%以上含まれている場合には、Zr含有量は0%でもよい。
また、Alは、チタン合金板のヤング率を増加させる元素でもある。ヤング率が増大することによって、銅箔製造ドラムの製造において、芯材とチタン合金板とが焼き嵌めされる際の焼き嵌め性が向上する。これにより、銅箔製造ドラムの生産性が向上する。また、ヤング率が増大することで、均一に焼き嵌められ、チタン合金板の研磨性が向上する。その結果、さらにマクロ模様の発生を抑制することが可能となる。
ヤング率を高めて焼き嵌め性を高める点からは、Al含有量を1.8%超とすることが好ましい。
一方、Alは、Sn又はZrと比較して、チタン合金板の高温強度をより増大させる。後述するように、本実施形態に係るチタン合金板を製造する際には、集合組織制御を目的に、熱間圧延を比較的低い温度まで実施する。そのため、高温強度が高くなりすぎると、熱間圧延時の反力が大きくなり、熱延後のチタン合金板の形状が大きく歪み、チタン合金板が波形状になる。そのため、チタン合金板に対しその後の矯正が多く必要となるが、その際にひずみが付与されると転位が多く導入されてしまう。この結果、チタン合金板をドラムに用いた際に、マクロ模様が発生しやすくなる。Al含有量が7.0%超であると靭性や加工性が低下してドラム製造が困難となる。その結果、銅箔製造ドラムの生産性が低下する。そのため、Al含有量を7.0%以下とする。上記の観点では、Al含有量は、3.0%以下とすることが好ましく、2.5%以下とすることがより好ましい。Alは、チタン合金板において必須ではないことから、Snおよび/またはZrが合計で0.2%以上含まれている場合には、Al含有量は0%でもよい。
本実施形態に係るチタン合金板は、Al含有量が1.8%超である場合において、Al含有量(平均含有量)を[Al%]としたときに、Alの濃度が([Al%]-0.2)質量%以上([Al%]+0.2)質量%以下である領域の面積率が、90%以上であることが好ましい。これにより、マクロ模様を安定的に抑制することができる。
Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] 式(1)
Al当量は、α相の安定化の程度を示す指標であり、Al当量が増加すると硬度が高くなる一方で靭性が低下する。Al当量を7.0質量%以下とすることで、靭性を維持することができ、焼き嵌め性を向上させることが可能となる。
Oは、チタン合金板の強度の向上に寄与し、表面硬度の増大に寄与する元素である。しかしながら、チタン合金板の強度が高くなりすぎると、強制時に比較的大きな加工が必要となり、双晶が発生しやすくなる。また、表面硬度が大きくなりすぎると、チタン合金板をドラムとした際に研磨が困難となる。したがって、チタン合金板にOが含有される場合、O含有量を0.700%以下とする。O含有量は0.400%以下とすることが好ましい。O含有量は、より好ましくは0.150%以下、さらに好ましくは0.120%以下である。Oは、チタン合金板において必須ではないことから、その含有量の下限は0%である。しかしながら、溶解原料であるスポンジチタンや添加元素からの混入を防ぐことは難しく、実質的な下限は0.020%である。
O含有量により強度向上効果を得る場合、O含有量は好ましくは、0.030%以上である。
Feは、β相を強化する元素である。チタン合金板においてはβ相の析出量が多くなるとマクロ模様の生成に影響を及ぼすので、チタン合金板にFeが含有される場合、Fe含有量の上限を0.500%とする。Fe含有量は、好ましくは0.100%以下、より好ましくは0.080%以下である。Feは、チタン合金板において必須ではないことから、その含有量の下限は0%である。しかしながら、実製造においてFeの混入を防ぐことは難しく、実質的な下限は0.001%である。
<C :0.080%以下>
<H :0.015%以下>
本実施形態に係るチタン合金板には、さらに、不純物として、N、C、又はHを含有しうる。
Nは、Tiと共に窒化物を形成する元素である。窒化物が形成されると、チタン合金板が硬化や脆化することがある。そのため、Nの含有は、極力抑制することが好ましい。本実施形態に係るチタン合金板では、N含有量を0.100%以下とする。N含有量は、好ましくは、0.080%以下である。Nは、チタン合金板において必須ではないことから、その含有量の下限は0%である。しかしながらNは、製造過程で混入する不純物であり、実質的なN含有量の下限を、0.0001%としてもよい。
ただし、上記の不純物には、β相安定化元素が含まれ得る。β相の析出量が多くなるとマクロ模様の発生に影響を及ぼすため、β相安定化元素は少ない方がよい。β相安定化元素として、例えば、V、Mo、Ta、Nb、Cr、Mn、Co、Ni、Cu等が挙げられる。本実施形態に係るチタン合金板では、不純物の含有量を合計で0.50%以下としたうえで、チタン合金板に含まれるβ相安定化元素それぞれの含有量が0.10%以下であることがより好ましい。
Al、Zr、SnやFe、V、Mo、Ta、Nb、Cr、Mn、Co、Ni、Cu等のβ安定化元素はIPC発光分光分析により測定することができる。OおよびNについては、酸素・窒素同時分析装置を用い、不活性ガス溶融、熱伝導度・赤外線吸収法により測定することができる。Cについては、炭素硫黄同時分析装置を用い、赤外線吸収法により測定することができる。Hについては、不活性ガス溶融、赤外線吸収法により測定することができる。
次に、本実施形態に係るチタン合金板の金属組織について説明する。
本実施形態に係るチタン合金板は、平均結晶粒径が40μm以下であり、結晶粒径(μm)の対数に基づく粒径分布の標準偏差が0.80以下であり、結晶構造が六方最密充填構造であるα相を含み、板厚方向に対するα相の[0001]方向のなす角が0°以上40°以下の結晶粒の面積率が70%以上である。
以下、本実施形態に係るチタン合金板の金属組織について、順を追って詳細に説明する。
本実施形態に係るチタン合金板の金属組織は、六方最密充填構造を有するα相を含む。本実施形態に係るチタン合金板の金属組織は、α相以外にβ相を含むことがある。しかしながら、β相は、α相よりも優先して腐食する。このため、β相を含むチタン合金板を表面に有するチタンドラムを銅箔の製造に用いた場合、β相が優先的に腐食されてドラム表面にマクロ模様が生じ、銅箔にそのマクロ模様が転写される可能性がある。また、β相が凝集して生成した場合、チタン合金板の集合組織が変化する可能性がある。そのため、β相が少ない方がよい。
本実施形態に係るチタン合金板におけるα相の体積率は、好ましくは、98.0%以上であり、より好ましくは、99.0%以上であり、さらに好ましくは、100%(α相単相)である。
上述したようなα相単相の金属組織は、上述したようなチタン合金板の化学組成により達成することができる。
次に、本実施形態に係るチタン合金板の金属組織に含まれる結晶粒の平均粒径及び粒径分布について説明する。
まず、チタン合金板の金属組織の結晶粒の粒径(結晶粒径)が粗大であると、その結晶粒そのものが模様となり、銅箔に模様が転写されるので、結晶粒径は微細な方が良い。チタン合金板の金属組織の結晶粒の平均結晶粒径が40μmを超えると、その結晶粒そのものが模様となり、銅箔に模様が転写されてしまう。このため、チタン合金板の金属組織の結晶粒の平均結晶粒径は、40μm以下とする。これにより、結晶粒が十分に微細となり、マクロ模様の発生が抑制される。チタン合金板の金属組織の結晶粒の平均結晶粒径は、好ましくは38μm以下、より好ましくは35μm以下である。
一方、チタン合金板の金属組織の結晶粒の平均結晶粒径の下限値は特に限定されない。しかしながら、結晶粒が非常に小さい場合には、熱処理時に未再結晶部が発生する恐れがある。このため、結晶粒の平均結晶粒径は、好ましくは3μm以上、より好ましくは5μm以上、さらに好ましくは10μm以上である。
一般に金属材料の結晶粒径分布は対数正規分布に従うことが知られている。したがって、上述したような粒径分布の標準偏差の算出に当たっては、得られた粒径分布を対数正規分布に規格化し、規格化した対数正規分布より標準偏差を算出してもよい。
<板厚方向に対するα相の[0001]方向のなす角が0°以上40°以下の結晶粒の面積率が70%以上>
チタンのα相の結晶構造は六方最密充填構造(hexagonal close-packed、hcp)をとる。hcp構造のチタンは、結晶方位による物性の異方性が大きい。具体的には、hcp構造のチタンでは、[0001]方向(以下c軸方向とも言う)に平行な方向では強度が高く、c軸方向と垂直な方向に近づくほど強度が低い。このため、チタン合金板が上述したような結晶粒の粒径分布を満足しても、例えば結晶方位の異なる結晶の集合体が発生すると、両集合体間での加工性が異なるため、銅箔製造ドラム製造時において、研磨時の加工性が異なってしまう場合がある。この場合、得られるドラムにおいて結晶粒に近いサイズでのマクロ模様として認識されてしまうおそれがある。そのため、チタン合金板の集合組織の結晶方位をできる限り集積させることにより、マクロ模様の発生を抑制することが好ましい。
NDとα相のc軸とのなす角θが40°以下の結晶粒の面積率が70%以上であることで、結晶方位が集積し、隣接する結晶間の結晶方位の差を小さくすることができる。その結果、マクロ模様を抑制できる。角θが40°以下の結晶粒の面積率は、全ての結晶粒の面積率に対し、好ましくは72%以上である。上記面積率は、高ければ高いほど良い。そのため、特に面積率の上限は定めないが、実質的に製造可能なのが95%程度までである。
例えば、図5に白色で示された領域G1は、NDとα相のc軸とのなす角θが40°以下の結晶粒を示し、黒色で示された領域G2は、α相のc軸とのなす角θが40°超60°未満の結晶粒を示し、灰色で示された領域G3は、α相のc軸とのなす角θが60°超90°以下の結晶粒を示している。そして、結晶方位解析により、(0001)極点図を作図することができる。図6に示すように、(0001)極点図において、点線b1で囲まれた領域R1は、板厚方向(ND)と結晶粒のc軸のなす角θが40°以下の領域であり、点線b1と点線b2とで囲まれた領域R2は、角θが40°超60°未満の領域であり、点線b2より外側の領域は、角θが60°以上90°以下の領域である。
圧延等によれば、結晶粒の集積度のピークは、最終圧延方向と直角な方向(最終圧延幅方向(TD))に傾きやすい。そのため、最終圧延方向が明確な場合には、板面の法線方向(ND)からの(0001)極点図において、結晶粒の集積度のピークが、板面の法線方向(ND)から最終圧延幅方向(TD)に30°以内に存在すればよい。
最大集積度は、大きい程好ましく、したがって上限は限定されないが、例えば熱間圧延により結晶方位を制御する場合、15~20程度が上限となりうる。
チタンでは塑性変形時に双晶変形を生じることがある。双晶変形は化学組成以外にも結晶粒径にも依存し、粒径が大きいほど発生し易い。そのため、双晶が生じることにより、見た目の結晶粒分布は均一になる場合がある。
一方で、双晶変形を生じると結晶方位差が大きくなり、結晶方位が大きく異なる結晶粒が隣接してしまい、その境界で研磨性が変化し模様として認識されるようになる。そのため、双晶は可能な限り抑制することが好ましい。
チタン合金板のドラム表面となる面の表面硬度(ビッカース硬さ)は、特に限定されないが、HV110以上であることが好ましい。これにより、チタン合金板を用いてドラムを製造し、表面を研磨する際に、均一な研磨が可能となり、マクロ模様をより一層抑制することができる。チタン合金板の表面硬度(ビッカース硬さ)は、より好ましくはHV112以上、さらに好ましくはHV115以上、である。
また、チタン合金板のドラム表面となる面の表面硬度(ビッカース硬さ)の上限は、特に限定されないが、表面硬度がHV350超であると、研磨の回数が増え、時間を要することになるため、ドラムの生産性が低下する。そのため、350HV以下であることが好ましい。より好ましくは300HV以下、さらに好ましくは、250HV以下である。また、チタン合金板の矯正時に必要な加工量を十分に小さくする場合、HV160以下であることが好ましい。より好ましくはHV155以下、さらに好ましくはHV150以下である。
本実施形態に係るチタン合金板の厚さは、特に限定されず、製造されるドラムの用途、仕様等に合わせて適宜設定することができる。銅箔製造ドラムの材料として用いられる場合、銅箔製造ドラムの使用に伴い、板厚が減少するため、チタン合金板の厚さは4.0mm以上とすることが好ましく、6.0mm以上としてもよい。チタン合金板の厚さの上限は、特に限定されないが、例えば、15.0mmである。
マクロ模様については、銅箔の製造工程で生じるが、チタン合金板におけるマクロ模様の生じやすさ(同一の条件でのマクロ模様の発生割合)については、チタン合金板の表面を#800のエメリー紙により研磨し、硝酸10%、ふっ酸5%溶液を用い表面を腐食させ、観察することで、評価できる。
以上説明したように、本実施形態に係るチタン合金板は、銅箔製造用のドラムに使用した際にマクロ模様の発生を十分に抑制可能であり、銅箔製造ドラムの材料として適している。
図8を参照し、本実施形態に係る銅箔製造ドラム20は、電着ドラムの一部であり、円筒状のインナードラム21と、前記インナードラム21の外周面に被着されたチタン合金板22と、前記チタン合金板22の突合せ部に設けられた溶接部23とを有し、前記チタン合金板22が、上述した本実施形態に係るチタン合金板である。
すなわち、本実施形態に係る銅箔製造ドラム20は、本実施形態に係るチタン合金板を用いて製造された銅箔製造ドラムである。本実施形態に係る銅箔製造ドラム20は、銅箔が析出するドラムの表面に、本実施形態に係るチタン合金板を用いているので、マクロ模様の発生が抑制され、高品質の銅箔を製造することができる。
本実施形態に係る銅箔製造ドラムのサイズは特段制限されないが、ドラムの直径は、例えば1~5mである。
インナードラム21は公知のものでよく、その素材は、チタン合金板でなくてもよく、例えば軟鋼やステンレス鋼でもよい。
チタン合金板22は、円筒状のインナードラム21の外周面に巻き付けられ、突合せ部を溶接されることで、インナードラムに被着される。そのため、突合せ部には溶接部23が存在する。
溶接部の金属組織の結晶粒の粒径(結晶粒径)が粗大であると、その結晶粒そのものが模様となり、銅箔に模様が転写される。溶接部の金属組織において結晶粒がこのように微細であることにより、結晶粒に起因する模様の発生が抑制される。
溶接部の金属組織は、α相主体である、すなわち、主としてα相を含む。β相は、α相よりも優先して腐食する。このため、均一な腐食を達成し、マクロ模様の発生を抑制する観点からは、β相は少ないほうが好ましい。一方で、β相が少量存在する場合、熱処理時の結晶粒成長を抑制できるため、均一かつ微細な結晶粒径を得ることができる。このような観点から、溶接部の金属組織は、β相の体積率は、2.0%以下であることが望ましい。この場合において、チタン合金板の金属組織の残部はα相である。β相の体積率は好ましくは1.0%以下であり、さらに好ましくは溶接部の集合組織はα単相である。また、本実施形態に係る溶接部の金属組織におけるα相の体積率は、好ましくは98.0%以上、より好ましくは99.0%以上、さらに好ましくは100%である。
以上説明した本実施形態に係るチタン合金板は、いかなる方法によって製造されてもよいが、例えば以下に説明する本実施形態に係るチタン合金板の製造方法により製造することができる。
本実施形態に係るチタン合金板の好ましい製造方法は、
(I)上述した化学組成を有するチタン合金を、750℃以上950℃以下の温度に加熱する第1の工程(加熱工程)と、
(II)加熱工程後に圧延し、チタン合金板とするする第2の工程(圧延工程)と、
(III)圧延工程後のチタン合金を焼鈍する第3の工程(焼鈍工程)と、
を有する。以下、各工程について説明する。
まず、上述した各工程に先立ち、チタン合金板の素材を準備する。素材としては、上述した化学組成のものを用いることができ、公知の方法により製造されたものを用いることができる。例えば、スポンジチタンから真空アーク再溶解法や電子ビーム溶解法又はプラズマ溶解法等のハース溶解法等の各種溶解法によりインゴットを作製する。次に、得られたインゴットをα相高温域やβ相単相域の温度で熱間鍛造又は圧延することにより、素材を得ることができる。素材には、必要に応じて洗浄処理、切削等の前処理が施されていてもよい。また、ハース溶解法で熱延可能な矩形のスラブ形状を製造した場合は、熱間鍛造等を行わず直接下記の第1の工程及び第2の工程(加熱、熱間圧延)に供してもよい。
本工程は、チタン材の熱間圧延に先立って行う加熱工程である。本工程においては、チタン合金板の素材を750℃以上950℃以下の温度に加熱する。加熱温度が750℃以上であることにより、第2の工程の熱間圧延においてチタン合金板の割れが発生することを防止できる。また、加熱温度が950℃以下であることにより、第2の工程の熱間圧延においてhcp構造のc軸が板幅方向に配向する集合組織(T-texture)が生成することを防止できる。
これに対し、加熱温度が750℃未満であると、例えば熱間鍛造、鋳造等において粗大粒子が生じている場合、第2の工程の熱間圧延において当該粗大粒子を起点としてチタン合金板に割れが発生してしまう場合がある。
さらに、板面の法線方向からの(0001)極点図において結晶粒の集積度のピークが最終圧延幅方向に対し30°以内に存在し、かつ、最大集積度が4.0以上である集合組織を得るためには、加熱温度は900℃以下であることが好ましく、特にAl含有量が3.0%以下の場合には、加熱温度は880℃以下が好ましい。
本工程では、加熱されたチタン合金板の素材を圧延(熱間圧延)する。そして、本工程において、合計の圧下率を80%以上とし、かつ、合計の圧下率のうち200℃以上650℃以下における圧延の圧下率の占める割合を、5%以上70%以下とすることが好ましい。これにより、結晶粒が上述したように均一に微細化され、また、hcp構造のc軸が板厚方向に沿って高度に集積した集合組織が得られる。本工程における熱間圧延開始温度は、基本的には上記加熱温度となる。
合計の圧下率が80%以上であることにより、熱間鍛造、鋳造等において生じた粗大粒を十分に微細化できるとともに、T-textureが発生することを防止することができる。合計の圧下率が80%未満であると、熱間鍛造、鋳造等において生じた組織が残存し、粗大粒を形成したり、T-textureが発生したりする場合がある。このような組織が生じた場合、製造されるドラムにおいてマクロ模様が発生してしまう。
本工程における合計の圧下率は、Al含有量3.0%以下の場合には、85%以上が好ましい。また、圧下率は、高ければ高いほど組織が良くなるので、必要とされる製品サイズ及び製造ミルの特性に合わせて定めればよい。
全圧延を650℃超で行った場合など、合計の圧下率のうち200℃以上650℃以下におけるチタン合金板の圧延の圧下率の占める割合が5%未満の場合、この温度域での圧下量が足りず、その後の冷却時に回復が生じ、ひずみ量が少ない部分が発生する。そのため、熱延後の熱処理により結晶粒径のバラつきが大きくなる。結晶粒径のバラツキは特に結晶粒成長を抑制するAl含有量が少ない場合に生じやすい。
また、200℃以上650℃以下におけるチタン合金板の圧延の圧下率の占める割合を、5%以上70%以下とすることで、結晶構造が六方最密充填構造であるα相を含み、板厚方向に対するα相の[0001]方向のなす角が0°以上40°以下の結晶粒の面積率が70%以上である組織、および/または板面の法線方向からの(0001)極点図において結晶粒の集積度のピークが最終圧延幅方向に対し30°以内に存在し、かつ、最大集積度が4.0以上である集合組織が得られやすくなる。
一方、全圧延を200℃未満で行った場合などで、合計の圧下率のうち200℃以上650℃以下におけるチタン合金板の圧延の圧下率の占める割合が5%未満の場合、板形状が不安定となる。この場合、その後の矯正における加工量が大きくなり、ひずみが導入され、矯正部とそれ以外の部分とでひずみ量の差が大きくなり、その後の熱処理で結晶粒径のばらつきが大きくなる。さらに、また、熱処理後に矯正すると、ひずみが影響し、その部分のみが腐食され易くなりマクロ模様の原因となる恐れがある。合計の圧下率のうち200℃以上650℃以下におけるチタン合金板の圧延の圧下率の占める割合は、好ましくは10%以上、より好ましくは15%以上である。
そのため、合計の圧下率のうち200℃以上650℃以下におけるチタン合金板の圧延の圧下率の占める割合は、70%以下が好ましい。より好ましくは65%以下、さらに好ましくは60%以下である。
具体的には、最終圧延方向での圧延による圧下率をL(%)、最終圧延方向と直交する方向での圧延による圧下率をT(%)とした際に、L/Tが1.0以上10.0以下であることが好ましい。これにより、得られるチタン合金板において、集合組織の集積度をより一層高めることができる。L/Tは、より好ましくは1.0以上5.0以下である。
冷間圧延を行う場合、予め熱間圧延後のチタン合金板表面の酸化スケールの除去を行う。酸化スケールの除去は、例えば、ショットブラスト、ショットブラストに続く酸洗によって行ってもよいし、切削などの機械加工によって行ってもよい。酸化スケールの除去前に、必要に応じて、β変態点未満の温度で焼鈍を行ってもよい。かかる焼鈍は、好ましくは(β変態点-50)℃以下で行う方がよい。
冷間圧延を行う場合、チタン合金板のAl含有量が多すぎると、冷延性に乏しく、チタン合金板が割れる可能性がある。そのため、冷間圧延を行う場合のチタン合金板のAl含有量は、3.5%以下であることが好ましい。
また、全結晶粒界長さに対する双晶粒界長さの割合を小さくする場合には、冷間圧延は行わないことが好ましい。
本工程では、チタン合金板を600℃以上β変態点℃以下の温度で20分以上の時間、熱処理(焼鈍)する。これにより、未再結晶粒を微細な再結晶粒として析出させることができ、得られるチタン合金板の金属組織中の結晶を均一かつ微粒にすることができる。この結果、マクロ模様の発生をより確実に抑制できる。
焼鈍時間の上限は特に限定されないが、例えば5時間以下である。特に結晶粒成長抑制効果を有するAl含有量が少ない場合などは、結晶粒の粗大化を抑制する観点から、焼鈍時間を90分以下とすることが好ましい。
また、焼鈍方法は、特段制限されず、連続式の加熱方式であってもよいし、バッチ式の加熱方式であってもよい。
後処理としては、酸洗や切削による酸化スケール等の除去や、洗浄処理等が挙げられ、必要に応じて適宜適用することができる。あるいは、後処理として、チタン合金板の矯正加工を行ってもよい。矯正加工は、例えば、真空クリープ矯正(VCF;Vacuum creep flattening)により行うことができる。
以上、本実施形態に係るチタン合金板の製造方法について説明した。
本実施形態に係る銅箔製造ドラムの製造方法は、円筒状に加工した本実施形態に係るチタン合金板の隣接する2つの端部を後述する溶接用チタン線材(本実施形態に係る溶接用チタン線材)を用いて溶接する工程(溶接工程)を有する。
チタン合金板の円筒状への加工、溶接条件等は、公知の方法とすることができる。
溶接に際しては、例えば、円筒状に加工したチタン合金板の隣接する2つの端部を上述した溶接用チタン線材を用いて肉盛り溶接し、溶接部(肉盛り溶接部)を形成する。ここで、溶接部に対し、冷間または温間による加工を行うため、肉盛り部に予盛りを行うことが好ましい。予盛りの厚さは、例えばチタン合金板の厚さの10~50%とすることができる。
また、肉盛り溶接部については、冷間または200℃以下の温間で圧下してもよい。これにより肉盛り溶接部の凝固組織を均一な微細等軸組織とすることができる。高い加工率による藁の発生を防止し、かつ凝固組織を確実に均一な微細等軸組織とするために、圧下率は、10%以上50%以下であることが好ましい。
また、溶接後に、熱処理(焼鈍)を行ってもよい。熱処理は、例えば500℃以上850℃以下の温度で、1分以上10分以下行うことができる。熱処理を850℃以下にて10分以下行うことにより、結晶粒の粗大化や、結晶粒の一部が粗大化することを防止し、均一な微粒結晶組織を得ることができる。
本実施形態に係る溶接用チタン線材は、銅箔製造チタンドラムの製造するために用いられることができ、より具体的には円筒状に曲げ加工したチタン合金板の隣接する端部を溶接するために用いられる。
Sn、ZrおよびAlからなる群から選択される1種以上:合計で0.2%以上6.0%以下
O :0.01%以上0.70%以下、
N :0.100%以下、
C :0.080%以下、
H :0.015%以下、および
Fe:0.500%以下、を含み、
残部がTiおよび不純物を含む化学組成を有することが好ましい。
一方、Snを過剰に添加すると化学組成によっては溶接用チタン線材の長手方向に偏析し、ビード溶接部に濃度由来のマクロ模様を形成する場合がある。このため、Sn含有量は、好ましくは6.0質量%以下であり、より好ましくは5.5質量%以下である。
一方、Zrを過剰に添加すると化学組成によっては変態温度付近のα+β域が広くなり、銅箔製造チタンドラムの製造時における熱処理においてβ相が析出しやすくなる。また、凝固偏析により表面の強度に差が生じる結果、銅箔製造チタンドラムの表面研磨時にマクロ模様が発生する場合がある。このため、Zr含有量は、好ましくは5.5質量%以下であり、より好ましくは5.0質量%以下である。
一方で、Al含有量が過剰であると、化学組成によっては高温強度の上昇が大きくなり、溶接用チタン線材の凝固組織(溶接部)の熱処理前の加工において反力が大きくなりすぎ加工割れが生じ得る、また、溶接部と母材との硬度の差が大きくなり、銅箔製造チタンドラムの研磨・整面時において段差が生じ得る。このため、Al含有量は、好ましくは5.0質量%以下、より好ましくは4.5質量%以下である。
このような場合、例えば、SnとAlとの合計の含有量は0.2質量%以上6.0質量%以下、好ましくは0.3質量%以上5.5質量%以下である。また、例えば、ZrとAlとの合計の含有量は、0.2質量%以上6.0質量%以下、好ましくは0.3質量%以上5.5質量%以下である。
一方、O含有量が0.70質量%超えると、溶接時に肉盛り加工での割れが生じてしまう。そのため、O含有量は0.70質量%以下である。O含有量は、好ましくは0.60質量%以下、より好ましくは0.50質量%以下である。
N、C、Hは、不純物であり、その含有量はそれぞれ低ければ低いほど好ましい。しかしながら、これらの元素は製造過程で混入する場合があり、実質的な含有量の下限を、Nで0.0001%、Cで0.0005%、Hで0.0005%としてもよい。
本実施形態に係る溶接用チタン線材の断面形状も、溶接に供することができる限り特に限定されるものではなく、任意の形状とすることができる。
まず、真空アーク再溶解法により表1、表2の化学組成を有するインゴットを作製し、これを熱間鍛造することにより、所定の組成のチタン合金板の素材を得た。
一部の例については、冷間圧延前焼鈍、冷間圧延を行った。
各発明例及び比較例に係るチタン合金板について、以下の項目について分析及び評価を行った。
各発明例及び比較例に係るチタン合金板の金属組織の結晶の平均結晶粒径D及び粒径分布の標準偏差は、以下のようにして測定、算出した。チタン合金板を切断した断面を化学研磨紙、電子線後方散乱回折法を用いて、2mm×2mmの領域を、2μmのステップで10視野測定した。その後、結晶粒径については、EBSDにより測定した結晶粒面積より円相当粒径(面積A=π×(粒径D/2)2)を求め、この個数基準の平均値を平均結晶粒径Dとし、さらに結晶粒径分布により対数正規分布における標準偏差σを算出した。
以下の方法で、チタン合金板の板厚方向(ND)とα相の[0001]方向(c軸)とのなす角θが40°以下の結晶粒の面積率を算出した。
チタン合金板を切断した断面を化学研磨し、EBSDを用いて結晶方位解析を行い。チタン合金板表面下部及び板厚中央部のそれぞれについて、2mm×2mmの領域をステップ2μmで10視野測定した。そのデータについて、TSLソリューションズ製のOIM Analysisソフトウェアを用いてNDとc軸とのなす角が40°以下である測定点データを抽出した。
Alの偏析の有無(Al均一性)について、以下のようにして確認した。EPMAにより、ビーム径を500μm、ステップサイズをビーム径と同じ500μmとし、チタン合金板の表面から板厚の1/4の位置における板厚方向に垂直な面20mm×20mm以上の領域について組成分析を行った。そして、組成分析結果を、合金元素濃度に換算するために、JIS1種工業用純チタン、及び対象とするチタン合金板を分析し、その結果から線形近似して得られた検量線を用いた。そして、Alの濃度が([Al%]-0.2)質量%以上([Al%]+0.2)質量%以下である領域の面積率を求めた。
各発明例及び比較例に係るチタン合金板の試料の厚さ方向断面を化学研磨し、電子線後方散乱回折法を用いて結晶方位解析した。具体的には、試料のチタン合金板の表面から板厚の1/4の位置において2mm×2mmの領域を、2μm間隔でスキャンし、逆極点図マップ(IPF:inverse pole figure)を作成した。その際、発生する(10-12)双晶、(10-11)双晶、(11-21)双晶、(11-22)双晶の回転軸及び結晶方位差(回転角)の理論値から2°以内を双晶界面とみなした。そして、結晶方位差(回転角)が2°以上の粒界を全結晶粒界長さとし、全結晶粒界長さに対する双晶粒界長さの割合を算出した。
各発明例及び比較例に係るチタン合金板の厚さ方向断面を鏡面研磨し、SEM/EPMAにより、表面から板厚の1/4の位置において、同断面におけるβ相安定化元素の濃度分布を測定し、β相安定化元素が濃化していない部分をα相の面積率とし算出した。
各発明例及び比較例に係るチタン合金板の表面硬度については、チタン合金板表面を鏡面となるまで研磨した後、JIS Z 2244:2009に準拠してビッカース硬さ試験機を用いて荷重1kgで3~5点測定し、得られた値を平均して、表面硬度とした。
マクロ模様については、5~10枚程度の50×100mmサイズの各発明例及び比較例に係るチタン合金板の表面を#800のエメリー紙により研磨し、硝酸10%、ふっ酸5%溶液を用い表面を腐食させることで観察した。次いで、3mm以上の長さ発生したスジ状の模様をマクロ模様とし、発生割合の平均に応じて下記のように評価を行った。
B:発生割合が1.0個/枚超5.0個/枚以下(良好、50×100mmの中に1.0個超5.0個以下)
C:発生割合が5.0個/枚超10.0個/枚以下(やや良好、50×100mmの中に5.0個超10.0個以下)
D:発生割合が10.0個/枚超(不合格、50×100mmの中に10.0個超)
得られた分析結果・評価結果を表5、表6に示す。
上述したマクロ模様観察のための#800のエメリー紙による研磨にて、研磨時間を1分として研磨を行った。研磨時間1分で表面肌が除去された場合、ドラム製造の生産性は維持されると判断し、研磨性が良好(OK)とし、1分で表面肌が除去できていない場合、ドラム製造の生産性を落とすことになると判断し、好ましくない(NG)とした。
焼き嵌め性については、以下のようにして評価した。焼き嵌め性はヤング率、形状比(例えば、管板であれば内管の外径と外管の内径の比)が影響する。特に、チタンを固定するために必要な応力を得るためには、チタンのヤング率が大きいほど小さな変形量で達成することができるため、加熱温度を下げることができ、作業性が向上する。そのため、ヤング率で135GPa以上の場合を焼き嵌め性に優れるとした。
0°以上40°以下の結晶粒の面積率(%)」は、板厚方向に対するα相のc軸のなす角が0°以上40°以下の結晶粒の面積率である。また、表2に示す「Al均一性(%)」は、Alの濃度が([Al%]-0.2)質量%以上([Al%]+0.2)質量%以下である領域の面積率である。また、表2に示す、「冷間圧延工程」における「RT」は、室温を意味する。
また、Al含有量の低い発明例1~16では、Al含有量の高い発明例101~発明例115に比べてマクロ模様の発生がより抑えられていた。一方で、Al含有量の高い発明例101~発明例115では、ヤング率が高く、焼き嵌め性に優れていた。
銅箔製造ドラムへの適用を想定し、表7に示す、上記実施例1の発明例と同様の方法で得られたチタン合金板を母材とし、直径1mの円筒状に加工した後、突合せ部(隣接する2つの端部)を表7に示す溶接用チタン線材を用いて溶接した。溶接は、予盛りの厚さを母材の板厚の25%以下とした。次いで、予盛り後に200℃以下の温度にて予盛分のみを母材厚さに減厚した。最後に溶接部を600~800℃、20~90分の条件で熱処理し、各発明例および各比較例に係る溶接用チタン線材による溶接サンプルを得た。
また、溶接部の金属組織に対し、SEM/EPMAを用いて、Feもしくはβ相安定化元素の濃度分布を測定し、Feの濃度またはβ相安定化元素の合計濃度が、測定範囲の平均濃度よりも1mass%以上高い点(濃化部)をβ相と定義し、面積率を求めた。面積率と体積率は等しいとして、得られた面積率をβ相の体積率、β相安定化元素が濃化していない部分(濃化部以外)の面積率をα相の体積率として、α相の体積率を求めた。
また、得られた各発明例および各比較例に係る溶接サンプル中の溶接部および母材のビッカース硬さ(Hv)を荷重1kgで3~5点測定し、その平均値により算出した。接触式の粗さ計を用いて、JISB0633:2001に従い、λc:0.8mm、λs:2.5μm、rtip:2μmで溶接部と母材部の境界の段差(μm)を測定した。
得られた各溶接サンプル中の溶接部のマクロ模様について、5~10枚程度の50×100mmサイズの各チタン合金板の表面を#800のバフにより研磨し、硝酸10%、ふっ酸5%溶液を用い表面を腐食後に観察した。次いで、3mm以上の長さで発生したスジ状の模様をマクロ模様とし、発生割合の平均に応じて下記のように評価を行った。
B:発生割合が1.0個/枚超5.0個/枚以下(良好、50×100mmの中に1.0個超5.0個以下)
C:発生割合が5.0個/枚超10.0個/枚以下(やや良好、50×100mmの中に5.0個超10.0個以下)
D:発生割合が10.0個/枚超(不合格、50×100mmの中に10.0個超)
更に、溶接部と母材部の境界に5μm以上の段差が生じた場合も、マクロ模様の欄にDで評価した。
結果を表8に示す。
2 電着ドラム
10 電解槽
30 電極板
40 巻取部
50 ガイドロール
60 巻取ロール
A 銅箔
20 銅箔製造ドラム
21 インナードラム
22 チタン合金板
23 溶接部
Claims (13)
- 質量%で、
Sn:0%以上2.0%以下、Zr:0%以上5.0%以下、及びAl:0%以上7.0%以下、からなる群より構成される1種又は2種以上:合計で0.2%以上7.0%以下、
N :0.100%以下、
C :0.080%以下、
H :0.015%以下、
O :0.700%以下、及び、
Fe:0.500%以下、を含有し、
残部がTi及び不純物を含有する化学組成を有し、
平均結晶粒径が40μm以下であり、
単位μmでの結晶粒径の対数に基づく粒径分布の標準偏差が0.80以下であり、
結晶構造が六方最密充填構造であるα相を含み、
板厚方向に対する前記α相の[0001]方向のなす角が0°以上40°以下の結晶粒の面積率が70%以上である、
チタン合金板。 - 板面の法線方向からの(0001)極点図において、電子線後方散乱回折法の球面調和関数法を用いた極点図の展開指数を16、ガウス半値幅を5°としたときのTexture解析により算出される集積度のピークが、前記板面の前記法線方向から30°以内に存在し、かつ、最大集積度が4.0以上である集合組織を有する、
請求項1に記載のチタン合金板。 - 前記平均結晶粒径を単位μmでDとした際に、前記粒径分布の標準偏差が、(0.35×lnD-0.42)以下である、請求項1または2に記載のチタン合金板。
- 板厚方向断面を観察した際に、表面から板厚1/4の位置における板厚断面の全結晶粒界長さに対する双晶粒界長さの割合が、5.0%以下である、請求項1~3のいずれか一項に記載のチタン合金板。
- 前記化学組成において、
Sn:0.2%以上2.0%以下、
Zr:0.2%以上5.0%以下、及び
Al:0.2%以上3.0%以下、からなる群より構成される1種又は2種以上を、合計で0.2%以上5.0%以下含有する、
請求項1~4のいずれか一項に記載のチタン合金板。 - 前記化学組成において、
Al:1.8%超7.0%以下を含有し、
ビッカース硬さが350Hv以下である、
請求項1~4のいずれか一項に記載のチタン合金板。 - 質量%での、Al含有量を[Al%]、Zr含有量を[Zr%]、Sn含有量を[Sn%]、O含有量を[O%]としたとき、下記式(1)、で示されるAl当量Aleqが、7.0以下である、
請求項6に記載のチタン合金板。
Aleq=[Al%]+[Zr%]/6+[Sn%]/3+10×[O%] 式(1) - 電子線マイクロアナライザを用いて、表面から板厚1/4の位置における板厚方向に垂直な面20mm×20mm以上の分析領域を組成分析したときに、Alの平均含有量を[Al%]として、前記分析領域の面積に対する、Alの濃度が([Al%]-0.2)質量%以上([Al%]+0.2)質量%以下である領域の面積率が90%以上である、請求項6または7に記載のチタン合金板。
- 前記α相を98.0体積%以上含有する、請求項1~8のいずれか一項に記載のチタン合金板。
- 銅箔製造ドラム用チタン合金板である、請求項1~9のいずれか一項に記載のチタン合金板。
- 円筒状のインナードラムと、
前記インナードラムの外周面に被着された、請求項1~10のいずれか一項に記載のチタン合金板と、
前記チタン合金板の突合せ部に設けられた溶接部と、
を有し、
前記溶接部の金属組織が、体積率で、98.0%以上のα相を有し、JIS G 0551:2013に準拠した粒度番号で、6以上11以下である、
銅箔製造ドラム。 - 円筒状に加工したチタン合金板の隣接する2つの端部を、溶接用チタン線材を用いて溶接する溶接工程を有し、
前記溶接用チタン線材が、質量%で、
Sn、ZrおよびAlからなる群から選択される1種以上:合計で0.2%以上6.0%以下、
O:0.01%以上0.70%以下、
N :0.100%以下、
C :0.080%以下、
H :0.015%以下、および
Fe:0.500%以下、を含み、
残部がTiおよび不純物を含む化学組成を有する、
銅箔製造ドラムの製造方法。 - 前記溶接用チタン線材において、前記Oの少なくとも一部が、Ti、Sn、ZrおよびAlからなる群から選択される1種以上の元素の酸化物として存在している、
請求項12に記載の銅箔製造ドラムの製造方法。
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