WO2017155072A1 - チタン材およびその製造方法 - Google Patents
チタン材およびその製造方法 Download PDFInfo
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- WO2017155072A1 WO2017155072A1 PCT/JP2017/009619 JP2017009619W WO2017155072A1 WO 2017155072 A1 WO2017155072 A1 WO 2017155072A1 JP 2017009619 W JP2017009619 W JP 2017009619W WO 2017155072 A1 WO2017155072 A1 WO 2017155072A1
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- titanium
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- 239000010936 titanium Substances 0.000 title claims abstract description 380
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 367
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 366
- 239000000463 material Substances 0.000 title claims abstract description 217
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- 239000010410 layer Substances 0.000 claims abstract description 119
- 239000002344 surface layer Substances 0.000 claims abstract description 110
- 239000000126 substance Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims description 8
- 238000005482 strain hardening Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 description 73
- 238000012856 packing Methods 0.000 description 41
- 238000000034 method Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 20
- 238000012545 processing Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- 238000005554 pickling Methods 0.000 description 14
- 239000011800 void material Substances 0.000 description 13
- 239000005022 packaging material Substances 0.000 description 11
- 238000005098 hot rolling Methods 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000005097 cold rolling Methods 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000879 optical micrograph Methods 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
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- 238000003384 imaging method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- 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
-
- 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
-
- 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
- B21B1/02—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 heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
-
- 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
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
- B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
- B23K20/021—Isostatic pressure welding
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
- B23K20/023—Thermo-compression bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2204/00—End product comprising different layers, coatings or parts of cermet
Definitions
- the present invention relates to a titanium material and a manufacturing method thereof.
- Titanium materials are utilized in seawater cooling condensers, heat exchangers, reactors, coolers, etc. for plants, taking advantage of their light weight and excellent corrosion resistance.
- the titanium material since the titanium material has a high specific strength, it is expected to be applied to a structural material used in a transportation engine such as an automobile or an aircraft for the purpose of improving fuel efficiency by reducing the weight.
- the value as a maintenance-free building material is increasing by making use of high specific strength and high corrosion resistance.
- a roof material for improving earthquake resistance a cover material for covering anticorrosion against seawater, and the like.
- the titanium material is being applied in various fields, but the titanium material is a very expensive material as compared with other steel materials. For this reason, it is necessary to reduce manufacturing costs in order to expand the application of titanium materials.
- titanium material is usually manufactured as follows. After chlorinating the raw material titanium oxide into titanium tetrachloride, magnesium (Krole method) or after reduction with sodium (Hunter method), a vacuum-separated process results in a bulky sponge metal titanium (sponge titanium) Manufactured.
- This sponge titanium is press-molded to form a titanium consumable electrode, and a titanium ingot is manufactured by vacuum arc melting using the titanium consumable electrode as an electrode.
- a titanium ingot is produced by dissolving sponge titanium in a water-cooled copper hearth by plasma or electron beam and continuously drawing it from a water-cooled copper mold.
- the titanium ingot manufactured by these methods is divided, forged, and rolled into a titanium slab (including so-called bloom and billet depending on the shape, etc.). Further, this titanium slab is subjected to hot rolling, annealing, pickling, cold rolling, and vacuum heat treatment to provide one, two, or three types as defined in JIS H4600 (titanium and titanium alloy-plates and strips). And four kinds of titanium materials are manufactured.
- the manufacturing process of the titanium sponge and the titanium ingot is a discontinuous batch type process, which increases the manufacturing cost. For this reason, in order to reduce the manufacturing cost of titanium, the technique of manufacturing titanium directly from sponge titanium, without passing through a melt
- Patent Document 1 discloses a titanium ingot (on a titanium slab) in which the surface of a porous titanium raw material (sponge titanium) formed into a rectangular parallelepiped shape is melted by using an electron beam under vacuum to make the surface layer portion dense titanium. A method for producing the equivalent) is disclosed. And a titanium material is manufactured by performing hot rolling and cold rolling to this titanium ingot. In the method disclosed in Patent Document 1, the porous titanium material has a porous portion formed into a slab shape and a dense coating portion that is formed of dense titanium and covers the porous portion. An ingot can be produced.
- magnesium chloride (hereinafter referred to as MgCl 2 ) inevitably remains in a titanium material manufactured without completely dissolving sponge titanium. Considering the adverse effect on the mechanical properties of the titanium material, it is preferable that the remaining amount of MgCl 2 is small. On the other hand, in order to reduce the content of MgCl 2 remaining inside the titanium material, it is necessary to increase the purity of the sponge titanium, which is a raw material, which may increase the cost.
- Patent Document 1 it is said that MgCl 2 can be volatilized and removed by irradiating sponge titanium with an electron beam. However, since it is necessary to irradiate an electron beam until heat is transferred to the inside, an increase in manufacturing cost is inevitable.
- Patent Document 1 since MgCl 2 inside is volatilized and removed, no study has been made on the influence of MgCl 2 remaining in the titanium material on the mechanical properties of the titanium material.
- a dense coating portion is formed by melting only the surface with an electron beam.
- Patent Document 1 describes a titanium ingot instead of a titanium slab, but it has a rectangular shape that does not require partial rolling, and is hereinafter referred to as a titanium slab.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide an inexpensive titanium material having excellent surface properties and ductility.
- the present invention is as listed below.
- a titanium material having an inner layer portion and a surface layer portion The chemical composition of the surface layer part is mass%, O: 0.40% or less, Fe: 0.50% or less, Cl: 0.020% or less, N: 0.050% or less, C: 0.080% or less, H: 0.013% or less, The balance: Ti and impurities,
- the chemical composition of the inner layer portion is mass%, O: 0.40% or less, Fe: 0.50% or less, Cl: more than 0.020, 0.60% or less, N: 0.050% or less, C: 0.080% or less, H: 0.013% or less, The balance: Ti and impurities,
- the inner layer portion has a gap, In the cross section perpendicular to the longitudinal direction of the titanium material, the area ratio of the voids in the inner layer portion is more than 0% and 30% or less, Satisfies the following formula (i): Titanium material.
- an inexpensive titanium material having excellent surface properties and ductility can be provided.
- FIG. 1 is a view for explaining the configuration of a titanium material according to an embodiment of the present invention.
- FIG. 2 is a structure photograph of a cross section of a titanium material according to an embodiment of the present invention.
- FIG. 3 is a view for explaining the configuration of a titanium material according to another embodiment of the present invention.
- FIG. 4 is a structure photograph of a cross section perpendicular to the longitudinal direction of the titanium material in the inner layer portion.
- FIG. 5 is a view for explaining the configuration of a titanium package that is a material of a titanium material according to an embodiment of the present invention.
- FIG. 6 is a diagram for explaining the configuration of the titanium casing.
- FIG. 7 is a diagram showing the relationship between the ratio of the surface layer thickness / inner layer thickness and the chlorine concentration (mass%) of the inner layer.
- the present inventors have conducted intensive studies from such a viewpoint. And the structure of the titanium material which was manufactured by hot processing (it is further cold-worked if needed) directly from sponge titanium without passing through a melt
- the amount of MgCl 2 remaining in the titanium material can be defined by the Cl content, which is a constituent element, because chlorine hardly dissolves in titanium. Based on this, the present inventors examined the relationship between the Cl content contained in the titanium material and the mechanical properties of the titanium material.
- the present inventors made the titanium material a structure having an inner layer portion and a surface layer portion joined thereto, and defined each Cl content, and further, according to the Cl content of the inner layer portion, the surface layer portion It was also found that by controlling the thickness of each of the inner layer portions, it is possible to prevent the deterioration of the mechanical characteristics without increasing the manufacturing cost. More specifically, it has been found that the higher the Cl content in the inner layer portion, the greater the thickness of the surface layer portion, thereby preventing the deterioration of the mechanical properties of titanium due to the mixed MgCl 2 .
- FIG. 1 is a view for explaining the configuration of a titanium material according to an embodiment of the present invention.
- the titanium material 1 has a surface layer portion 2 and an inner layer portion 3.
- the surface layer portion 2 is bonded to both surfaces of the inner layer portion 3.
- FIG. 2 is a structural photograph of a cross section of the titanium material. 2 that the surface layer 2 and the inner layer 3 can be clearly distinguished. Further, it can be seen that the thickness of the surface layer portion 2 is constant within ⁇ 15% and is excellent in surface properties.
- the titanium material 1 is a plate material, but is not limited thereto, and may be, for example, a round bar material or a wire material.
- FIG. 3 is a view for explaining the configuration of a titanium material according to another embodiment of the present invention. As shown in FIG. 3, in the case where the titanium material 1 is a round bar or wire, the surface layer portion 2 is joined so as to cover the entire circumference of the columnar inner layer portion 3.
- the chemical components of the surface layer portion 2 are as defined in the four types of JIS H4600 except for Cl.
- the specific chemical components are O: 0.40% or less, Fe: 0.50% or less, Cl: 0.020% or less, N: 0.050% or less, C: 0.080% or less, and H : 0.013% or less.
- the Cl content in the surface layer portion 2 can be improved.
- O may be 0.30% or less, 0.10% or less, 0.050% or less, 0.010% or less, or 0.0060% or less.
- Fe may be 0.30% or less, 0.20% or less, 0.10% or less, 0.070% or less, or 0.050% or less.
- Cl may be 0.018% or less, 0.015% or less, 0.012% or less, or 0.009% or less.
- N may be 0.040% or less, 0.030% or less, 0.010% or less, 0.005% or less, or 0.001% or less.
- C may be 0.040% or less, 0.020% or less, 0.010% or less, 0.007% or less, 0.005% or less, or 0.002% or less.
- H may be 0.010% or less, 0.005% or less, 0.003% or less, or 0.002% or less. There is no particular need to define these lower limits, and the lower limit is 0%.
- the balance is Ti and impurities.
- the impurity element Sn, Mo, V, Mn, Nb, Mg, Si, Cu, Co, Pd, Ru, Ta, which are mainly mixed from sponge titanium or scrap which is a raw material of the surface packaging material 5 described later, Examples include Y, La, Ce and the like.
- the content of these impurity elements in JIS H4600, but it is preferable to reduce it as much as possible.
- the total content combined with O, N, C, Fe and H described above is 5% or less, the inclusion of these impurities does not hinder the mechanical properties targeted by the present invention.
- the total content may be 1% or less, 0.50% or less, or 0.20% or less, or 0.10% or less. Further, the total content of impurity elements may be 2% or less, 1% or less, 0.50% or less, 0.20% or less, or 0.10% or less.
- the target mechanical property here means that the total elongation when the tensile test is performed in a direction parallel to the processing direction of the titanium material 1 is 20% or more.
- the surface layer portion 2 is formed by rolling a titanium plate or the like, there is basically no void. That is, the area ratio of the voids in the surface layer portion 2 (hereinafter, also simply referred to as void ratio, the definition and measurement method thereof will be described later) is 0%.
- the porosity of the surface layer portion 2 may be less than 0.10%, less than 0.050%, or less than 0.010%.
- Inner layer 3 The inner layer portion 3 is in accordance with four types of JIS H4600, except for Cl.
- the specific chemical components are: O: 0.40% or less, Fe: 0.50% or less, and Cl: more than 0.020%, 0.60% or less, N: 0.050% or less, C: 0 0.080% or less, and H: 0.013% or less.
- a raw material with low purity titanium for the inner layer portion 3.
- a raw material with high purity titanium has a low Cl content in the production process.
- a raw material having a low Cl content is expensive because titanium has a high purity.
- the Cl content of the inner layer portion 3 exceeds 0.60%, even if the Cl content of the surface layer portion 2 is reduced, the tensile properties and bendability of the titanium material 1 are significantly deteriorated.
- O may be 0.15% or less, 0.10% or less, 0.050% or less, 0.010% or less, or 0.006% or less.
- Fe may be 0.30% or less, 0.20% or less, 0.10% or less, 0.070% or less, or 0.050% or less.
- the lower limit of Cl may be 0.025%, 0.030%, 0.040%, or 0.050%, and the upper limit of Cl is 0.15%, 0.35%, or 0.55% Also good.
- N may be 0.040% or less, 0.030% or less, 0.010% or less, 0.005% or less, or 0.001% or less.
- C may be 0.040% or less, 0.020% or less, 0.010% or less, 0.007% or less, 0.005% or less, or 0.002% or less.
- H may be 0.010% or less, 0.005% or less, 0.003% or less, or 0.002% or less. There is no particular need to define these lower limits, and the lower limit is 0%.
- the balance is Ti and impurities.
- impurity elements mainly include Sn, Mo, V, Mn, Nb, Mg, Si, Cu, Co, Pd, Ru, Ta, Y, La, Ce, and the like as impurity elements mixed from sponge titanium.
- Mg is mixed as MgCl 2 .
- the total content may be 1% or less, 0.5% or less, or 0.2% or less, or 0.1% or less. Further, the total content of impurity elements may be 2% or less, 1% or less, 0.50% or less, 0.20% or less, or 0.10% or less.
- the chemical composition of the surface layer portion 2 and the inner layer portion 3 is measured by the following method.
- Component analysis of the surface layer part 2 and the inner layer part 3 is performed by a known method (for example, JIS H 1612 (1993), JIS H 1614 (1995), JIS H 1615 (1997), JIS H 1617 (1995), JIS H 1619 ( 2012), JIS H 1620 (1995)).
- a known method for example, JIS H 1612 (1993), JIS H 1614 (1995), JIS H 1615 (1997), JIS H 1617 (1995), JIS H 1619 ( 2012), JIS H 1620 (1995)).
- the surface layer portion 2 and the inner layer portion 3 are cut out from the titanium material 1 and measured. It is more efficient to analyze the surface layer part 2 from chips obtained by machining or the like, and the inner layer part 3 from the remaining material after the surface layer is deleted.
- the entire component analysis of the titanium material 1 is performed, and the analysis value and either the surface layer portion 1 or the inner layer portion 3
- the component of the surface layer may be calculated (reverse calculation) from these analysis values and the respective plate thicknesses. Moreover, it does not interfere with the component analysis of the surface layer part 1 or the inner layer part 3 by EPMA or the like.
- FIG. 4 is a structure photograph observing a cross section perpendicular to the longitudinal direction of the titanium material 1 in the inner layer portion 3.
- the inner layer portion 3 has voids. This void is inevitably included in the manufacturing process. In order to completely eliminate the voids, it is necessary to perform processing under a large pressure, which restricts the shape and dimensions of the titanium material 1 and causes a rise in manufacturing cost. On the other hand, since the density of the inner layer part 3 becomes low by having a space
- the area ratio of the voids in the inner layer portion 3 in the cross section perpendicular to the longitudinal direction of the titanium material 1 is set to more than 0% and 30% or less.
- the area ratio of the voids observed in the cross section perpendicular to the longitudinal direction of the titanium material 1 is also referred to as the void ratio.
- the porosity may be 10% or less, 5% or less, 2% or less, 1% or less, or 0.5% or less.
- the porosity of the inner layer portion 3 can be selected according to the application, and is lower when the mechanical properties of the titanium material 1 are important, while higher when weight reduction is prioritized. Good.
- the porosity is more preferably 5% or less, further preferably 3% or less, and particularly preferably 1% or less.
- the lower limit of the porosity is more than 0%, but may be 0.01%, 0.05%, or 0.1% as necessary.
- the porosity p is obtained by the following procedure. First, an observation sample is cut out from the titanium material 1. When the titanium material 1 is thick, an observation sample is cut out from the center of the thickness of the inner layer portion 3. Then, the cut specimen for observation is embedded in a resin so that a cross section perpendicular to the longitudinal direction of the titanium material 1 becomes an observation face, and then buffed with a diamond or alumina suspension to be mirror finished. . Then, a photograph is taken with an optical microscope of the observation surface that has been mirror-finished at the center of the thickness of the titanium material 1.
- the void ratio is obtained by measuring the area of the void included in the photographed optical micrograph and dividing it by the area of the entire photographing field. At this time, photographing with an optical microscope is performed so that the total observation area is 0.3 mm 2 or more (20 fields of view or more in an optical microscope photograph with a magnification of 500 times), and an average value thereof is adopted.
- the microscope used for the observation is not a problem even with a normal optical microscope, but it is desirable to use it because it can be observed more clearly by using a differential interference microscope capable of observing polarized light.
- the thickness of the surface layer portion 2 and the inner layer portion 3 and the Cl content of the inner layer portion 3 are controlled so as to satisfy the following formula (i).
- the meaning of each symbol in the above formula (i) is as follows.
- Cl I Cl content (mass%) in the inner layer t S : surface layer thickness t I : inner layer thickness
- the thickness of the surface layer portion 2 is the thickness of the portion indicated by 2-1 or 2-2 in FIG.
- the thinner one that is, the smaller thickness is set.
- the thickness of the surface layer portion 2 is the thickness of the portion indicated by 2 in FIG.
- the surface layer part 2 and the inner layer part 3 have different microstructures and crystal grain sizes. Therefore, as shown in FIG. 2, the boundary between the surface layer portion 2 and the inner layer portion 3 can be clearly distinguished by polishing and etching a cross section perpendicular to the rolling direction of the titanium material. And the thickness of the surface layer part 2 and the inner layer part 3 of the titanium material 1 is each measured from the structure
- MgCl 2 is distributed according to the amount of Cl contained, and the surface layer portion 2 and the inner layer portion 3 may be distinguished on the basis of the presence or absence of this MgCl 2 .
- the inner layer portion has a Cl content of more than 0.020% and 0.60% or less
- the surface layer portion has a Cl content of 0.020% or less
- the Cl content of the inner layer portion is greater than that of the surface layer portion. Higher than Cl content.
- the inner layer portion and the surface layer portion can also be discriminated from the difference in Cl concentration.
- the difference in Cl concentration between the inner layer portion and the surface layer portion is also clarified by observing the element distribution state of Cl by measuring EPMA after mirror-polishing the cross section as shown in FIG.
- the thickness of the surface layer portion 2 is preferably 0.01 to 35 mm while satisfying the above (i).
- the thickness of the surface layer portion 2 is smaller than 0.01 mm, the surface layer portion 2 becomes too thin when the titanium material 1 is manufactured, and the inner layer portion may be exposed on the surface.
- the lower limit of the thickness of the surface layer portion 2 may be 0.05 mm, 0.10 mm, 0.15 mm, or 0.20 mm.
- the upper limit of the thickness of the surface layer portion 2 is determined by the thickness of the titanium material 1 and the lower limit thickness of the inner layer portion.
- the upper limit of the thickness of the surface layer portion 2 may be 0.30 mm, 0.50 mm, 1.0 mm, 3.0 mm, 10 mm, or 20 mm.
- the thickness of the inner layer part 3 is preferably 0.01 to 90 mm while satisfying the above (i).
- the lower limit of the thickness of the inner layer part 3 may be 0.05 mm, 0.10 mm, 0.20 mm, 0.50 mm, or 0.70 mm.
- the upper limit of the thickness of the inner layer portion 3 is determined by the thickness of the titanium material 1 and the lower limit thickness of the surface layer portion.
- the upper limit of the thickness of the inner layer part 3 may be 0.90 mm, 1.2 mm, 1.5 mm, 2.0 mm, 5.0 mm, 10 mm, 20 mm, or 50 mm.
- the thickness of the titanium material 1 is 0.03 mm or more while satisfying the above (i).
- the thickness of the titanium material 1 may be 0.10 mm or more, 0.30 mm or more, or 0.50 mm or more. Further, the thickness of the titanium material 1 may be 20 mm or less, 50 mm or less, or 100 mm or less as long as the above (i) is satisfied. However, considering the cost, the thickness of the titanium material 1 is preferably 15 mm or less while satisfying the above (i).
- the thickness of the titanium material 1 may be 10 mm or less, 5.0 mm or less, 4.0 mm or less, 2.0 mm or less, 1.5 mm or less, or 1.2 mm or less.
- FIG. 5 is a view for explaining the configuration of a titanium package 4 that is a material of the titanium material 1 according to an embodiment of the present invention.
- a titanium case 6 made of sponge titanium or briquette obtained by compressing sponge titanium is filled in a titanium casing constituted by the surface packing material 5.
- FIG. 6 is a diagram for explaining the configuration of the titanium casing.
- the titanium casing In the example shown in FIG. 6, it is assembled in a box shape using five plate-shaped surface layer packing materials 5, and only the upper surface is open. The upper surface can be sealed with another plate-shaped surface packaging material 5 (not shown).
- a state in which the packaging material 5 shown in FIG. 6 is assembled is referred to as a titanium case.
- the titanium lump 6 is in the state where the circumference
- the titanium housing is box-shaped, but the shape is not limited, and may be tubular, or may be a shape in which a plate material and a tube material are combined.
- the titanium material 1 is obtained by performing hot working or the like (for example, hot rolling or cold rolling) on the titanium package 4. That is, the surface layer packing material 5 and the titanium lump 6 of the titanium package 4 correspond to the surface layer portion 2 and the inner layer portion 3 of the titanium material 1 after hot working, respectively.
- sponge titanium and briquettes in a state where the inside of the titanium casing is filled are collectively referred to as a titanium lump 6.
- the degree of vacuum (absolute pressure) inside the titanium package 4 is set to 10 Pa or less in order to prevent the titanium lump 6 from being oxidized and nitrided during high-temperature heating and holding during hot working.
- the internal degree of vacuum is preferably 1 Pa or less. There is no particular lower limit on the internal pressure. However, if the degree of vacuum is made extremely small, it leads to an increase in manufacturing cost such as improvement of the air tightness of the device or enhancement of the vacuum exhaust device. For this reason, the degree of vacuum is preferably 1 ⁇ 10 ⁇ 3 Pa or more.
- the degree of vacuum inside the surface layer packing material 5 indicates the degree of vacuum in a region (also referred to as a gap) excluding the titanium block 6 in the region surrounded by the surface layer packing material 5.
- the section perpendicular to the hot working direction has a quadrangular shape.
- the present invention is not limited to this, and when the material of the titanium material 1 that is a round bar or wire is used, the cross section perpendicular to the rolling direction of the titanium package 4 may be circular or polygonal.
- the chemical composition of the surface packing material 5 is the same as the chemical composition of the surface layer portion 2 of the titanium material 1 described in 1-2.
- the shape of the titanium material used as the surface packaging material 5 depends on the shape of the titanium packaging 4. For this reason, the surface packing material 5 has no particular shape, and is, for example, a plate material or a pipe material. However, in order to ensure the hot workability and cold workability of the titanium package 4 and to make the titanium material 1 have excellent surface properties, ductility, and bendability, it is used for the surface packaging material 5. It is necessary to adjust the thickness of the plate material or the thickness of the pipe material. Hereinafter, the thickness of the plate material or the thickness of the tube material used for the surface layer packing material 5 is simply referred to as “thickness of the surface layer packing material 5”.
- the surface layer packing material 5 breaks in the course of hot working due to plastic deformation and the vacuum breaks, leading to oxidation of the titanium mass 6 inside. .
- the undulation of the sponge titanium filled in the titanium package 4 is transferred to the surface of the surface packing material 5, and a large surface undulation is generated on the surface of the titanium package 4 during hot working.
- the surface properties of the manufactured titanium material 1 and mechanical properties such as ductility are adversely affected.
- the thickness of the surface packaging material 5 is 0.5 mm or more.
- the thickness of the surface layer packing material 5 is preferably 1.0 mm or more, and more preferably 2.0 mm or more.
- the packing material is assembled by welding to form a titanium casing or a titanium packing body. In order to ensure the strength of the welded portion, the thickness is 70 mm or less.
- the thickness of the surface layer packing material 5 may be 30 mm or less, 10 mm or less, or 5.0 mm or less.
- the thickness of the surface layer packing material 5 is preferably 40% or less or 20% or less of the total thickness of the titanium package 4.
- Titanium chunk 6 The chemical composition of the titanium block 6 is the same as the chemical composition of the inner layer 3 of the titanium material 1 described in 1-3.
- a titanium block having a component range defined as one, two, three, or four types of JIS H4600 can be used except for Cl.
- the specific chemical components are: O: 0.40% or less, Fe: 0.50% or less, and Cl: more than 0.020%, 0.60% or less, N: 0.050% or less, C: 0 0.080% or less, and H: 0.013% or less.
- O may be 0.15% or less, 0.10% or less, 0.050% or less, 0.010% or less, or 0.006% or less.
- Fe may be 0.30% or less, 0.20% or less, 0.10% or less, 0.070% or less, or 0.050% or less.
- the lower limit of Cl may be 0.025%, 0.030%, 0.040%, or 0.050%, and the upper limit of Cl is 0.15%, 0.35%, or 0.55% Also good.
- N may be 0.040% or less, 0.030% or less, 0.010% or less, 0.005% or less, or 0.001% or less.
- C may be 0.040% or less, 0.020% or less, 0.010% or less, 0.007% or less, 0.005% or less, or 0.002% or less.
- H may be 0.010% or less, 0.005% or less, 0.003% or less, or 0.002% or less.
- the titanium block 6 may contain elements exemplified by Sn, Mo, V, Mn, Nb, Mg, Si, Cu, Co, Pd, Ru, Ta, Y, La, and Ce as impurities. Good.
- a low-purity titanium lump 6 containing 0.020% or more of Cl is used as a raw material in order to produce an inexpensive titanium material 1.
- Cl content of the titanium lump 6 exceeds 0.60%, the hot workability and cold workability of the titanium package 4 are lowered, and the surface properties and mechanical properties of the titanium material 1 to be manufactured are reduced. to degrade.
- a. Sponge titanium b.
- One or more selected from briquettes obtained by compressing sponge titanium can be used.
- Sponge titanium is a normal sponge titanium produced by a conventional smelting process such as a crawl method reduced with magnesium.
- JIS H2151, 1 type M, 2 type M, 3 type M, or 4 type M Sponge titanium having a chemical composition corresponding to the above can be used.
- Sponge titanium is generally in the shape of a flake, and the size varies depending on the production process, but the average particle size is about several tens of millimeters. In this invention, it is preferable that the average particle diameter of sponge titanium is 30 mm or less. This is because when the average particle size of the sponge titanium is larger than 30 mm, a problem may occur in handling during transportation or during manufacture of the titanium package 4.
- the particle size of the sponge titanium is preferably 30 mm or less.
- the average particle size of the sponge titanium is small, there is no problem in terms of characteristics, but when it is too small, the generation of dust when filling the titanium casing formed of the surface packaging material 5 becomes a problem. There is a risk of hindering work. For this reason, it is preferable that the average particle diameter of sponge titanium is 1 mm or more.
- Sponge titanium is indefinite, and it is preferable to use briquettes obtained by compressing sponge titanium as a titanium lump because handling becomes easy.
- sponge titanium as a raw material is put into a mold prepared in advance, and compression processing is performed at a predetermined pressure. To manufacture. At this time, titanium scrap or the like may be mixed in the sponge titanium, but it is preferable to mix well in advance so that there is no fluctuation in the components of the titanium mass.
- the lower limit value of the thickness ratio X of the titanium material 1 can be determined from the measured amount of Cl in the titanium mass.
- the target X value is determined in consideration of the Cl amount measurement accuracy, the allowance for the thickness of the surface layer portion in consideration of the surface flaws in the titanium material 1, the variation in manufacturing, and the like.
- the thickness ratio X between the surface layer portion and the inner layer portion of the titanium material 1 is represented by the following formula from its definition.
- X ts / ti (2)
- the thickness ts of the surface layer part and the thickness ti of the inner layer part of the titanium material 1 are expressed by the following expressions from the expressions (1) and (2), respectively.
- ts X ⁇ t / (2X + 1)
- ti t / (2X + 1) (4)
- the thickness ts2 of the surface layer portion and the thickness ti2 of the inner layer portion of the hot-rolled material before pickling are as follows.
- the ratio Z between the thickness of the surface layer portion and the thickness of the inner layer portion of the hot-rolled material before pickling is as follows.
- the porosity of the inner layer of hot-rolled material is often less than 1% and is very low. For this reason, the porosity can often be ignored industrially or practically.
- Ts can be calculated using the above formula (13) or (14).
- the substantial thickness D of the titanium block 6 excluding the voids is provisionally determined based on restrictions on the dimensions of the package 4.
- the thickness of the surface layer portion of the titanium packing 4 (the thickness of the surface packing material 5) Ts is determined.
- the target X value was predicted from the measurement result of the chlorine content of the sponge titanium as a raw material, the chlorine content of the titanium mass 6 produced was measured, ii) It is preferable to confirm that the formula is satisfied. If necessary, the thickness (the thickness of the surface packing material 5) Ts of the surface layer portion of the titanium package 4 is changed so as to satisfy the formula (ii).
- the bottom and side portions of the titanium casing are assembled into a box shape using five titanium plates (surface packing materials) as shown in FIG. Is in an open state. Then, the titanium casing is filled with sponge titanium and / or briquettes in which sponge titanium is compression-molded in advance, and then a titanium plate (surface packing material) that hits the upper surface of the titanium casing is covered from above and temporarily assembled.
- the titanium casing is box-shaped, but the shape is not limited and may be tubular.
- the temporarily assembled titanium casing is housed in a vacuum chamber, the vacuum degree in the chamber is reduced to 10 Pa or less, and the joint portion is welded to form the titanium package 4.
- sponge titanium normal sponge titanium manufactured by the smelting process of a crawl method is used. However, it is necessary to adjust so that the Cl content in the sponge titanium falls within the above-mentioned specified range.
- Sponge titanium produced by the crawl method is produced by reducing titanium tetrachloride with Mg. MgCl 2 produced by this reduction is removed by the next vacuum separation step.
- MgCl 2 is not completely removed, and some of the inevitable impurities remain in the crushed sponge titanium.
- the vacuum reseparation process described below can be performed.
- the vacuum re-separation treatment is a heat treatment in a vacuum atmosphere maintained at 900 to 1200 ° C. in a vacuum environment having a degree of vacuum of 1.3 Pa or less (more preferably 1.3 ⁇ 10 ⁇ 2 Pa or less). Can be adjusted according to the desired Cl content and the Cl content of the raw sponge titanium. For example, when obtaining sponge titanium having a Cl content of 0.05% or less, it is preferable to heat in a vacuum of 1.3 ⁇ 10 ⁇ 2 Pa or less for 40 hours or more.
- the method for welding the joint portion of the titanium casing is not particularly limited.
- arc welding such as TIG welding or MIG welding, electron beam welding, or laser welding may be used.
- welding is performed in a vacuum atmosphere or an inert gas atmosphere so that the surfaces of the titanium block 6 and the surface packing material 5 are not oxidized or nitrided.
- the plate-shaped titanium material 1 is obtained by hot-rolling the above-mentioned titanium package 4. In addition, although hot rolling is performed when obtaining the plate-shaped titanium material 1, hot extrusion processing etc. should just be performed when obtaining the round bar-shaped or wire-shaped titanium material 1.
- FIG. 1 A block diagram illustrating an exemplary computing environment in accordance with the present disclosure.
- the surface oxide layer may be removed by pickling, etc., and then cold rolling may be performed to make the film thinner.
- the heating temperature at the time of hot working may be the same as that at the time of hot working a conventional titanium slab or billet created by casting.
- the heating temperature is preferably 600 to 1200 ° C., depending on the size of the titanium package 4 or the processing rate.
- the hot working rate is preferably set to 50% or more in order to bond sponge titanium to each other to reduce voids and ensure sufficient mechanical properties.
- the titanium material 1 can contain voids within a range where mechanical properties such as strength and ductility are allowed.
- the hot working rate at this time can be selected in consideration of desired mechanical characteristics. At this time, the hot working rate is preferably 30% or more and 50% or less.
- an appropriate cold working rate can be selected according to the shape of the final product.
- the cold working rate is preferably 30% or more and 95% or less.
- the cold working rate may be 96% or 98% or less.
- Further annealing may be performed after hot working and cold working.
- the annealing is preferably performed at a temperature of 500 to 850 ° C. in a vacuum or in an inert gas atmosphere, and the annealing time can be selected according to the required mechanical properties.
- the processing rate during hot processing or cold processing is the ratio (percentage) obtained by dividing the difference in cross-sectional area before and after processing by the cross-sectional area before processing.
- a B is the cross-sectional area after processing
- a A it is defined as follows.
- the cross-sectional area in this case is a cross-sectional area of a cross section perpendicular
- vertical to a process (rolling) direction. Processing rate (%) (A B ⁇ A A ) / A B ⁇ 100
- Titanium cases were filled with sponge titanium (Cl: 0.021 to 0.502%, average particle size: 0.25 to 19 mm) produced by the crawl method and having different Cl contents.
- sponge titanium Cl: 0.021 to 0.502%, average particle size: 0.25 to 19 mm
- a cuboid titanium case having a thickness of 75 mm, a width of 100 mm, and a length of 120 mm was manufactured using a titanium plate (JIS type 1) having a thickness of 0.6 to 36 mm.
- titanium plates surface packing materials
- the titanium plate was covered and temporarily assembled as a titanium casing.
- the temporarily assembled titanium case is housed in a vacuum chamber and the internal vacuum is reduced to 8.2 ⁇ 10 ⁇ 3 to 1.1 ⁇ 10 ⁇ 1 Pa. It was welded and sealed with an electron beam to obtain a titanium package.
- this titanium package was heated to 850 ° C. in an air atmosphere, and then hot-rolled to obtain a hot-rolled sheet having a thickness of 5 mm. Thereafter, pickling treatment (descaling treatment) was performed to remove about 50 ⁇ m per side (100 ⁇ m on both sides) on both sides of the hot-rolled sheet using shot blasting and nitric hydrofluoric acid.
- pickling treatment was performed to remove about 50 ⁇ m per side (100 ⁇ m on both sides) on both sides of the hot-rolled sheet using shot blasting and nitric hydrofluoric acid.
- the hot-rolled sheet was cold-rolled to obtain a titanium plate having a thickness of 1 mm.
- the titanium material was produced by performing the heat processing which heats to 670 degreeC in a vacuum or inert gas atmosphere as annealing treatment, and hold
- the lower limit value 0 of X was calculated from the analysis result 0.023% of the amount of chlorine in sponge titanium.
- the thickness of the titanium material was 1 mm, and the target X value was set to 0.75 in consideration of the occurrence of surface flaws and the like.
- a target value of 17.2 mm for the substantial thickness D of the titanium block excluding voids and a target value of 13.3 mm for the thickness Ts of the surface packaging material were provisionally determined. Calculate the required volume of the titanium case from the weight of the titanium block from the substantial thickness D of the titanium block and the porosity when the titanium case is filled with sponge titanium, and the thickness inside the titanium case (in the titanium package) was 48.4 mm.
- a titanium package having a thickness of 75 mm was manufactured using the titanium block and the titanium plate.
- the chemical composition of the surface layer part and the inner layer part is JIS H 1612 (1993), JIS H 1614 (1995), JIS H 1615 (1997), JIS H 1617 (1995), JIS H 1619 (2012), JIS H 1620 (1995). ) And measured.
- the chemical composition of the portion was analyzed using a chip obtained by machining or the like.
- the chemical component of the portion is determined from the analysis result of the entire chemical component of the titanium material and the analysis result of the chemical component of the thicker (inner layer portion or surface layer portion). was calculated.
- the thickness of the surface layer portion and the inner layer portion was measured by microstructural observation with an optical microscope. First, after embedding in resin so that the cross section of the produced titanium material could be observed, and polishing and corrosion, an optical micrograph was taken. As shown in FIG. 2, boundary lines can be clearly observed in the surface layer portion and the inner layer portion. In addition, since the difference in density after corrosion is observed due to the difference in crystal grain size or the like, the boundary can also be determined by this.
- the thickness of the surface layer part and the inner layer part is measured from 20 randomly selected cross-sectional photographs, the average value of each part is obtained, and from the measured average thickness of the surface layer part and the inner layer part, the thickness of the surface layer part / The thickness of the inner layer portion was calculated.
- the porosity of the inner layer portion of the titanium material was determined as follows. First, an observation sample was cut out from the central portion of the inner layer. Then, the cut-out observation sample was embedded in a resin so that a cross section perpendicular to the longitudinal direction of the titanium material became an observation surface, and then buffed with a diamond or alumina suspension to give a mirror finish. Then, an optical micrograph of the observation surface that was mirror-finished was taken.
- the area of the void portion included in the photographed optical micrograph was measured, and the void ratio was obtained by dividing the area by the area of the entire field of view.
- photography with the optical microscope was performed so that an observation area might be 0.3 mm ⁇ 2 > or more in total (20 visual fields or more with the optical microscope photograph of 500 times magnification), and those average values were employ
- a strip-shaped test piece having a width of 20 mm and a length of 50 mm is cut out from the manufactured titanium material having a thickness of 1 mm in parallel with the rolling direction, and flat plate is bent 180 ° according to JIS Z 2248 (2014) (metal material bending test method). A test (diameter inside the bend is the plate thickness) was performed, and the bendability was evaluated based on the presence or absence of cracks.
- Test numbers 1 to 15 in Tables 1 and 2 are examples of the present invention that satisfy all the conditions defined in the present invention.
- the inner layer portion has a Cl content of 0.60% or less, satisfies the formula (i), and further satisfies the void volume ratio of 30% or less. Excellent results.
- test numbers 16 to 37 are comparative examples that do not satisfy the conditions defined in the present invention.
- the Cl content of the inner layer portion was 0.60% or less, since the formula (i) was not satisfied, the ductility or bendability was inferior.
- FIG. 7 shows an example of the present invention as “B” and a comparative example as “X” regarding bendability.
- the examples of the present invention have good bendability even when the chlorine concentration in the inner layer portion is high. As described above, by appropriately controlling the surface layer thickness and the inner layer thickness, the deterioration of the mechanical characteristics due to Cl is prevented.
- a titanium packaging body having a thickness of 39 to 148 mm, a width of 100 mm, and a length of 120 mm was manufactured by the same manufacturing method as in Example 1 using a 4.0 mm thick titanium plate (JIS type 1) as a surface layer packaging material. Produced.
- this titanium package 4 was heated to 850 ° C. in an air atmosphere, and then hot-rolled to obtain a hot-rolled sheet having a thickness of 20 mm. Thereafter, using a shot blast and nitric hydrofluoric acid, a descaling process was performed to remove about 50 ⁇ m per side (100 ⁇ m on both sides) on both sides of the hot-rolled sheet, and a titanium material was manufactured.
- the chemical composition, thickness, and mechanical properties of the titanium material of the surface layer portion and the inner layer portion were investigated by the same evaluation method as in Example 1.
- the surface properties of the titanium material were visually observed to evaluate the presence or absence of surface cracks, and those with no cracks were rated as “ ⁇ ” and those with cracks as “X”.
- JIS H 4600 (2012) a bending test was not required for a titanium material having a thickness of 5 mm or more, and the bending test was not performed in this example.
- Test numbers 38 to 42 in Tables 3 and 4 are examples of the present invention that satisfy all the conditions defined in the present invention.
- the Cl content of the inner layer portion is 0.60% or less, satisfies the formula (i), and further satisfies the void volume ratio of 30% or less. The result was excellent in ductility.
- the titanium package was subjected to hot rolling, descaling, cold rolling, and annealing treatment by the same manufacturing method as in Example 1 to produce a titanium material.
- test number 55 a hole was made in one end of the surface packing material in advance and a copper tube was soldered. The whole package was assembled, and the seam of the surface packing material was arc-welded all around in an Ar gas atmosphere to assemble a titanium package. Then, after the pressure inside the titanium package was reduced to 15 Pa through the copper tube, the copper tube was sealed to produce a titanium package. Thereafter, hot rolling and cold rolling were performed in the same manner as in the above example to obtain a titanium material.
- the chemical composition, thickness, and mechanical properties of the titanium material of the surface layer portion and the inner layer portion were investigated by the same evaluation method as in Example 1. Also in this example, when the total elongation was 20% or more, it was determined that the ductility was excellent. Furthermore, the surface properties of the titanium material were visually observed to evaluate the presence or absence of surface cracks, and those with no cracks were rated as “ ⁇ ” and those with cracks as “X”.
- Test numbers 43 to 50 in Tables 5 and 6 are examples of the present invention that satisfy all the conditions defined in the present invention.
- the Cl content of the inner layer portion is 0.60% or less, satisfies the formula (i), and further satisfies the void volume ratio of 30% or less. The result was excellent in ductility.
- Test Nos. 51 to 54 were inferior in bendability because the Cl content of the inner layer was 0.60% or less but did not satisfy the formula (i).
- Test No. 55 had good surface properties, but the inner layer portion was partially oxidized and the O content deviated from the specification, resulting in low ductility and poor bendability.
- the titanium material according to the present invention has excellent surface properties, elongation, and bendability, and is suitable for use in members that require high deformability, such as roof tiles. .
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Abstract
Description
前記表層部の化学組成が、質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物であり、
前記内層部の化学組成が、質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020超、0.60%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物であり、
前記内層部は空隙を有し、
前記チタン材の長手方向に垂直な断面において、前記内層部の前記空隙の面積率が、0%を超えて30%以下であり、
下記(i)式を満足する、
チタン材。
ClI≦0.03+0.02×tS/tI ・・・(i)
但し、上記(i)式中の各記号の意味は以下のとおりである。
ClI:内層部のCl含有量(質量%)
tS:表層部の厚さ
tI:内層部の厚さ
質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物である化学組成を有するチタン筐体を作製する工程と、
前記チタン筐体の内部に、
質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020超、0.60%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物である化学組成を有するスポンジチタンおよび該スポンジチタンを圧縮したブリケットから選択される1種以上を充填する工程と、
前記チタン筐体の内部の真空度を10Pa以下にした後、該内部の真空度が維持されるように周囲を密閉し、チタン梱包体とする工程と、
前記チタン梱包体に対して、熱間加工を行う工程と、を備える、
チタン材の製造方法。
上記(2)に記載のチタン材の製造方法。
1-1.全体構成
図1は、本発明の一実施形態に係るチタン材の構成を説明するための図である。図1に示すように、チタン材1は、表層部2および内層部3を有する。本実施形態においては、内層部3の両面にそれぞれ表層部2が接合されている。また、図2は、チタン材の断面を観察した組織写真である。図2からも表層部2と内層部3とが明瞭に区別できることが分かる。さらに、表層部2の厚さはその変動が±15%以内で一定であり、表面性状に優れることが見て取れる。
表層部2の化学成分は、Clを除き、JIS H4600の4種の規定どおりとする。その具体的な化学成分は、O:0.40%以下、Fe:0.50%以下、Cl:0.020%以下、N:0.050%以下、C:0.080%以下、およびH:0.013%以下とする。特に、表層部2におけるCl含有量を0.020%以下に制限することによって、チタン材1としての延性を向上させることが可能になる。
内層部3は、Clを除き、JIS H4600の4種の規定どおりとする。その具体的な化学成分は、O:0.40%以下、Fe:0.50%以下、およびCl:0.020%超、0.60%以下、N:0.050%以下、C:0.080%以下、およびH:0.013%以下とする。
p(%)=内層部中に存在する空隙の面積/内層部の面積 × 100
本発明においては、内層部3のCl含有量が高いほど、内層部3の厚さに対する表層部2の厚さの割合を大きくすることにより、MgCl2に起因した、チタン材1全体での機械的特性の劣化を防止する。
ClI≦0.03+0.02×tS/tI ・・・(i)
但し、上記(i)式中の各記号の意味は以下のとおりである。
ClI:内層部のCl含有量(質量%)
tS:表層部の厚さ
tI:内層部の厚さ
2-1.全体構成
図5は、本発明の一実施形態に係るチタン材1の素材であるチタン梱包体4の構成を説明するための図である。図5に示すように、チタン梱包体4は、表層梱包材5で構成されたチタン筐体の内部に、スポンジチタン、またはスポンジチタンを圧縮して得られたブリケットからなるチタン塊6が満たされた構造を有する。
表層梱包材5の化学成分は、前記1-2で記載したチタン材1の表層部2の化学成分と同じとする。表層梱包材5には、JIS H4600の1種、2種、3種または4種のチタンを用いることができる。
チタン塊6の化学成分は、前記1-3で記載したチタン材1内層部3の化学成分と同じとする。チタン塊6には、Clを除き、JIS H4600の1種、2種、3種または4種として定められた成分範囲のチタン塊を用いることができる。その具体的な化学成分は、O:0.40%以下、Fe:0.50%以下、およびCl:0.020%超、0.60%以下、N:0.050%以下、C:0.080%以下、およびH:0.013%以下とする。
チタン梱包体4に対して熱間加工を施して製造されるチタン材1が上述した(i)式を満足するためには、チタン梱包体4の寸法の調整が重要となる。このためには、まず(i)式をもとに、チタン材1の表層部の厚さts、チタン材1の内層部の厚さtiとの比X(=ts/ti)の目標値を決定することが、好ましい。その一例を、次に述べる。
X≧(ClI-0.03)/0.02・・・・・・・・・・(ii)
ただし、X<0の場合、X=0とする。
目標のX値に基づきチタン梱包体4の寸法を決定する方法の一例を、下記に示す。まず、チタン材1の厚さをt、チタン材1の表層部の厚さをts、チタン材1の内層部の厚さをtiとすると、tは下記式となる。
t=2ts+ti・・・・・・・・・(1)
X=ts/ti・・・・・(2)
チタン材1の表層部の厚さtsおよび内層部の厚さtiは、(1)および(2)式から、それぞれ下記の式であらわされる。
ts=X・t/(2X+1)・・・・・・・(3)
ti=t/(2X+1)・・・・・・・・・・(4)
t3=t2-2te・・・・・・・(5)
ts3=X・t3/(2X+1)・・・・・・・(6)
ti3=t3/(2X+1)・・・・・・・・・(7)
ts2=ts3+te
=X・t3/(2X+1)+te・・・・・(8)
ti2=ti3
=t3/(2X+1)・・・・・・・・・・(9)
Z=ts2/ti2
={X・t3/(2X+1)+te}/{t3/(2X+1)}
=X+te(2X+1)/t3・・・・・(10)
Z=X+α(2X+1)・・・・・・・・・(11)
V=Z
Ts/D=X+α(2X+1)・・・・・・・(12)
Ts={X+α(2X+1)}D・・・・・(13)
Ts={X+0.01(2X+1)}D・・・・・(14)
D=W/BLρ・・・・・・・・・・・・・・・・(15)
D=Ti(1-P)・・・・・・・・・・・・・・・・(16)
Ts=(0.75+0.01(1+2×0.75))×17.16=13.3mm
つまり、Ts=13.3mmとなった。Ti=48.4mmであり、T=13.3×2+48.4=75mm厚の梱包体となる。
本発明の一実施形態に係るチタン梱包体4およびチタン材1の製造方法の一例について説明する。なお、以下の説明においては、板状のチタン材1の製造方法を一例として用いているが、これに限定されるものではない。
まず、チタン筐体の底面、および側面に相当する部分を、図6に示すように、5枚のチタン板(表層梱包材)を用いて箱型に組み立て、上面のみが開口した状態とする。そして、チタン筐体の内部に、スポンジチタンおよび/または予めスポンジチタンを圧縮成形したブリケットを充填し、その後、チタン筐体の上面に当たるチタン板(表層梱包材)を上から被せ、仮組みする。なお、上記の例では、チタン筐体は箱型であるが、形状は制限されず、管状などであってもよい。
上述のチタン梱包体4に対して、熱間圧延を行うことによって板状のチタン材1が得られる。なお、板状のチタン材1を得る場合には、熱間圧延を行うが、丸棒状または線材状のチタン材1を得たい場合には、熱間押し出し加工などを施せばよい。
加工率(%)=(AB-AA)/AB×100
チタン筐体に、クロール法により製造したCl含有量が異なるスポンジチタン(Cl:0.021~0.502%、平均粒径:0.25~19mm)を充填した。ここで、厚さ0.6~36mmのチタン板(JIS1種)を用いて、厚さ75mm、幅100mm、長さ120mmの直方体状のチタン筐体を製作した。
表層部および内層部の化学組成は、JIS H 1612(1993)、JIS H 1614(1995)、JIS H 1615(1997)、JIS H 1617(1995)、JIS H 1619(2012)、JIS H 1620(1995)に準拠して測定した。なお、この際、表層部または内層部の厚さが0.2~0.1mmの場合、その部分の化学組成は、切削等で加工して得た切粉等を用いて分析を行った。表層部または内層部の厚さが0.1mm未満の場合、チタン材の全体の化学成分の分析結果と、厚い方(内層部または表層部)の化学成分の分析結果から、当該部分の化学成分を算出した。
表層部および内層部の厚さは、光学顕微鏡によるミクロ組織観察により測定を行なった。まず、作製したチタン材の断面を観察できるように樹脂に埋め込み、研磨・腐食した後に、光学顕微鏡写真を撮影した。図2に示したように、表層部および内層部には、境界線がはっきりと観察できる。加えて、結晶粒径の差等により、腐食後の濃淡に差がみられるため、これにより境界を判別することもできる。
チタン材の内層部の空隙率は、次のように求めた。まず、内層部の板厚中心部から観察用試料を切り出した。そして、チタン材の長手方向に垂直な断面が観察面となるように、切り出された観察用試料を樹脂に埋め込んだ後、ダイヤモンドまたはアルミナ研濁液を用いてバフ研磨して鏡面化仕上げした。そして、鏡面化仕上げした観察面の光学顕微写真を撮影した。
作製したチタン材から、圧延方向に平行部12.5×60mm(厚さ=板厚)、標点間50mm、チャック部20mm幅、全長150mmの引張試験材(JIS13B引張試験片)を切り出し、JIS Z 2241(2011)(金属材料引張試験方法)に従って平板引張試験を行い、全伸びにより延性を評価した。なお、本実施例においては、全伸びが20%以上である場合に、延性に優れると判断することとした。
チタン筐体に、クロール法により製造したスポンジチタン(Cl:0.025%、平均粒径=0.25~19mm)を充填した。また、表層梱包材として、厚さ4.0mmのチタン板(JIS1種)を用いて、実施例1と同様の製造方法で、厚さ39~148mm、幅100mm、長さ120mmのチタン梱包体を製作した。
クロール法により製造したスポンジチタン(Cl:0.028~0.052%、平均粒径=0.25~19mm)を金型に入れて圧縮プレスして、かさ密度3.2g/cm3のブリケットに成形した。
2 表層部
3 内層部
4 チタン梱包体
5 表層梱包材
6 チタン塊
Claims (3)
- 内層部と表層部とを有するチタン材であって、
前記表層部の化学組成が、質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物であり、
前記内層部の化学組成が、質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020超、0.60%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物であり、
前記内層部は空隙を有し、
前記チタン材の長手方向に垂直な断面において、前記内層部の前記空隙の面積率が、0%を超えて30%以下であり、
下記(i)式を満足する、
チタン材。
ClI≦0.03+0.02×tS/tI ・・・(i)
但し、上記(i)式中の各記号の意味は以下のとおりである。
ClI:内層部のCl含有量(質量%)
tS:表層部の厚さ
tI:内層部の厚さ - 請求項1に記載のチタン材を製造する方法であって、
質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物である化学組成を有するチタン筐体を作製する工程と、
前記チタン筐体の内部に、
質量%で、
O:0.40%以下、
Fe:0.50%以下、
Cl:0.020超、0.60%以下、
N:0.050%以下、
C:0.080%以下、
H:0.013%以下、
残部:Tiおよび不純物である化学組成を有するスポンジチタンおよび該スポンジチタンを圧縮したブリケットから選択される1種以上を充填する工程と、
前記チタン筐体の内部の真空度を10Pa以下にした後、該内部の真空度が維持されるように周囲を密閉し、チタン梱包体とする工程と、
前記チタン梱包体に対して、熱間加工を行う工程と、を備える、
チタン材の製造方法。 - 前記熱間加工を行う工程の後に、さらに冷間加工および焼鈍を行う工程を備える、
請求項2に記載のチタン材の製造方法。
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2017
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- 2017-03-09 WO PCT/JP2017/009619 patent/WO2017155072A1/ja active Application Filing
- 2017-03-09 JP JP2017535118A patent/JP6206628B1/ja active Active
- 2017-03-09 US US16/082,289 patent/US11542581B2/en active Active
- 2017-03-09 KR KR1020187029218A patent/KR102157279B1/ko active IP Right Grant
- 2017-03-09 CN CN201780016749.7A patent/CN108883447B/zh active Active
- 2017-03-09 EP EP17763412.8A patent/EP3427850B1/en active Active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2021080519A (ja) * | 2019-11-19 | 2021-05-27 | 日本製鉄株式会社 | α+β型チタン合金棒材及びα+β型チタン合金棒材の製造方法 |
JP7448777B2 (ja) | 2019-11-19 | 2024-03-13 | 日本製鉄株式会社 | α+β型チタン合金棒材及びα+β型チタン合金棒材の製造方法 |
CN116372075A (zh) * | 2023-02-07 | 2023-07-04 | 贵州锆石科技发展有限责任公司 | 钛合金整体盘轴锻件3d打印坯料的真空等温锻造方法 |
Also Published As
Publication number | Publication date |
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RU2699338C1 (ru) | 2019-09-04 |
KR102157279B1 (ko) | 2020-09-17 |
US20190032183A1 (en) | 2019-01-31 |
TWI619815B (zh) | 2018-04-01 |
JPWO2017155072A1 (ja) | 2018-03-22 |
CN108883447A (zh) | 2018-11-23 |
EP3427850A1 (en) | 2019-01-16 |
KR20180123523A (ko) | 2018-11-16 |
JP6206628B1 (ja) | 2017-10-04 |
EP3427850A4 (en) | 2019-08-14 |
CN108883447B (zh) | 2020-03-24 |
TW201804002A (zh) | 2018-02-01 |
US11542581B2 (en) | 2023-01-03 |
EP3427850B1 (en) | 2020-12-30 |
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