WO2017171056A1 - Titanium composite material and method for manufacturing same, and package - Google Patents
Titanium composite material and method for manufacturing same, and package Download PDFInfo
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- WO2017171056A1 WO2017171056A1 PCT/JP2017/013754 JP2017013754W WO2017171056A1 WO 2017171056 A1 WO2017171056 A1 WO 2017171056A1 JP 2017013754 W JP2017013754 W JP 2017013754W WO 2017171056 A1 WO2017171056 A1 WO 2017171056A1
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- titanium
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- 239000010936 titanium Substances 0.000 title claims abstract description 383
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 379
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 367
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- 238000000034 method Methods 0.000 title description 33
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- 150000004767 nitrides Chemical class 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 144
- 239000010410 layer Substances 0.000 claims description 97
- 239000000843 powder Substances 0.000 claims description 59
- 238000012856 packing Methods 0.000 claims description 57
- 239000002344 surface layer Substances 0.000 claims description 38
- 239000012535 impurity Substances 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 15
- 239000004484 Briquette Substances 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 11
- 238000005482 strain hardening Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 229910052742 iron Inorganic materials 0.000 description 16
- 229940125936 compound 42 Drugs 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000003466 welding Methods 0.000 description 15
- 239000000470 constituent Substances 0.000 description 14
- 238000005098 hot rolling Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000011162 core material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005242 forging Methods 0.000 description 8
- 238000009864 tensile test Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000000304 warm extrusion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- 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
- B22F7/02—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
- B22F7/04—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 with one or more layers not made from powder, e.g. made from solid metal
-
- 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
Definitions
- the present invention relates to a titanium composite material, a manufacturing method thereof, and a package.
- Titanium is a metal material with excellent corrosion resistance, and is used in heat exchangers using seawater, various chemical plants, and the like. Moreover, since the density is smaller than that of carbon steel and excellent in specific strength (strength per unit weight), it is often used in aircraft bodies. In addition, by using titanium material for land transportation equipment such as automobiles, the land transportation equipment itself is light and expected to improve fuel efficiency.
- titanium materials are more complicated than steel materials and are manufactured through many processes.
- a typical manufacturing process is illustrated below.
- Smelting process Titanium oxide as a raw material is chlorinated to titanium tetrachloride, and then reduced with magnesium or sodium to form sponge-like (lumped) metal titanium (hereinafter referred to as “sponge titanium”).
- Manufacturing process (2) Melting process: Titanium sponge is press-molded to form an electrode and melted in a vacuum arc melting furnace to produce an ingot.
- Hot working process A slab or billet is heated and rolled or extruded hot to produce a plate or a round shape (hot rolled material) or billet (material such as hot extrusion or hot rolling) Steps for manufacturing bars, etc.
- Cold working step Steps for producing thin plates, round bars, wires, etc. by further cold rolling and extruding plates and round bars.
- Titanium material is very expensive because it is manufactured in many processes. For this reason, titanium materials are hardly applied to land transportation equipment such as automobiles. For this reason, in order to promote utilization of the titanium material, it is necessary to increase the productivity of the manufacturing process. In order to cope with this problem, efforts have been made to simplify the manufacturing process of the titanium material.
- Patent Document 1 discloses a method for producing a titanium thin plate by forming a composition containing titanium powder, a binder, a plasticizer, and a solvent into a thin plate shape, drying, sintering, compacting, and re-sintering. . According to this method, the melting step, the forging step, the hot rolling step, and the cold rolling step can be omitted.
- Patent Document 2 discloses a method of manufacturing a titanium alloy round bar by adding copper powder, chromium powder or iron powder to titanium alloy powder, enclosing it in a carbon steel capsule, heating and extruding it hot. It is disclosed. According to this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
- Patent Document 3 discloses a method of manufacturing a round bar by filling sponge titanium powder in a copper capsule, heating to 700 ° C. or lower, and performing a warm extrusion process. In this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
- conventionally known pack rolling is a method in which a core material such as a titanium alloy having poor workability is covered with a cover material such as inexpensive carbon steel having good workability and hot rolling is performed.
- a core material such as a titanium alloy having poor workability
- a cover material such as inexpensive carbon steel having good workability and hot rolling is performed.
- the release agent is applied to the surface of the core material, at least two upper and lower surfaces thereof are covered with a cover material, or in addition to the upper and lower surfaces, four peripheral surfaces are also covered with a cover material, and a seam is welded and hermetically covered A box is manufactured, the inside of which is evacuated and sealed, and then hot rolled.
- Patent Document 4 discloses a method for assembling a hermetically sealed box
- Patent Document 5 discloses that a cover material is sealed (packed) at a vacuum degree of 10 ⁇ 3 torr (about 0.133 Pa) or more. Further, a method for producing a hermetically sealed box is disclosed. Further, Patent Document 6 covers carbon steel (cover material) and performs high energy density welding under a vacuum of 10 ⁇ 2 torr (about 1.33 Pa) or less. A method for producing a hermetically sealed box by sealing (packing) is disclosed.
- the core material which is the material to be rolled
- the core material is covered with a cover material and hot-rolled, so the surface of the core material does not come into direct contact with the cold medium (air or roll), and the temperature of the core material decreases. Therefore, even a core material with poor workability can be manufactured.
- cover material carbon steel, etc., which is different from the core material, has good workability and is inexpensive. Since the cover material becomes unnecessary after hot rolling, a release agent is applied to the surface of the core material in order to facilitate separation from the core material.
- Patent Document 1 an expensive titanium powder (average particle size of 4 to 200 ⁇ m) is used as a raw material, and many processes such as sintering and compaction are required. Is very expensive and has not yet promoted the use of titanium.
- Patent Documents 4 to 6 are stripped and discarded after rolling as in pack rolling, the manufacturing cost is higher than that in a normal process, and the obtained titanium material has a high The cost remains the same.
- an object of the present invention is to provide a titanium material such as a titanium plate or a titanium round bar at a low cost.
- amorphous and sponge-like (lumped) sponge titanium is used as a raw material. Since sponge-like sponge titanium has been conventionally produced, it can be obtained at a relatively low cost. In addition, since titanium sponge has main impurities such as iron and chlorine removed in the smelting process, there is no problem in chemical composition even if a titanium material is directly produced from sponge titanium. Moreover, titanium materials (hereinafter referred to as “titanium scrap”) such as mill ends that cannot be manufactured can be obtained at a relatively low cost. However, since titanium scrap is indefinite, it cannot be directly processed to produce a titanium material.
- (B) If it is a titanium package that contains a filler such as sponge titanium in a container (hereinafter referred to as “packaging material”) manufactured using a pure industrial titanium material or a titanium alloy material, Generation of surface defects such as surface cracks and shavings can be suppressed during the hot working.
- packing material a filler such as sponge titanium in a container
- the chemical composition of the filler the same type as that of pure titanium material, it is not necessary to peel off and discard the cover material after rolling as in conventional pack rolling. Can also be used effectively as part of a titanium composite (product).
- (E) That is, selected from carbon, carbide, nitride, and oxide that can increase the tensile strength of titanium sponge and titanium composite material in the titanium packing material that is an expanded material of industrial pure titanium Fill and enclose one or more powders, depressurize the inside to form a titanium package, perform hot working on this titanium package, and further cold work as necessary to obtain a titanium composite.
- the titanium package which is a collection of titanium ingots before hot working, becomes a titanium composite material (three-layer clad material) that is compressed and integrated as a whole after hot working.
- the titanium composite is a compression-molded body of titanium containing only one or more titanium compounds selected from carbides, nitrides and oxides whose only inner layer portion can increase the tensile strength of the titanium composite.
- the surface layer is a wrought material of industrial pure titanium or titanium alloy material, it has excellent workability and high tensile strength, and can be manufactured without the conventional melting process and forging process. Can be greatly reduced.
- the present invention is as listed below.
- a titanium composite material having an inner layer portion and a surface layer portion covering the inner layer portion is made of an industrial pure titanium material or a titanium alloy material having a chemical composition belonging to any one of JIS types 1 to 4,
- one or more kinds of titanium compounds selected from carbide, nitride and oxide are dispersed in titanium, carbon around the carbide, nitrogen around the nitride, and the oxidation Oxygen around each object has a portion where each diffuses, and the area ratio has voids of more than 0% and not more than 30%. Titanium composite.
- the inner layer portion has a total content of carbon, nitrogen and oxygen of 0.05 to 2.0% by mass, and the titanium compound is formed into a titanium material as a streak compound aggregate in which the titanium compounds are arranged in the rolling direction.
- the chemical composition of the industrial pure titanium material is mass%, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, Balance: Ti and impurities,
- Titanium packing material made of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4, one or more selected from sponge titanium, titanium briquette and titanium scrap, and carbon, carbide, nitriding Filled with one or more powders selected from products and oxides, sealed, and reduced in pressure to 10 Pa or less inside to form a titanium package, and hot processing the titanium package, A method for producing a titanium composite material.
- a packing body comprising a titanium packing material made of an industrial pure titanium material or a titanium alloy material belonging to any one of JIS 1-4, and a filler filled in the titanium packing material,
- the filler has at least one selected from sponge titanium, titanium briquette and titanium scrap, and at least one powder selected from carbon, carbide, nitride and oxide, and the internal pressure is 10 Pa or less, Package for hot working.
- the titanium composite material according to the present invention is excellent in mechanical properties such as tensile strength and Young's modulus, and can be manufactured without undergoing a melting step, a forging step, and the like, so that the manufacturing cost can be greatly reduced.
- the titanium composite material according to the present invention includes a large amount of titanium material such as cutting and removal of many defective portions on the surface layer and bottom surface of the ingot, and removal of surface cracks and badly shaped front and rear ends (crop) after forging. Since it can manufacture without performing cutting removal and cutting removal, a manufacturing yield improves significantly and the manufacturing cost is also reduced significantly also from this point.
- FIG. 1 is an explanatory view showing an example of the configuration of a titanium composite material according to the present invention.
- FIG. 2 is a diagram schematically showing the streak-like compound aggregate 42a.
- FIG. 4 is an explanatory view showing an example of a configuration of a titanium package that is a material for hot working of a titanium composite material according to the present invention.
- FIG. 5 is an explanatory view showing an example of the structure of the titanium briquette.
- FIG. 6 is an explanatory view showing an example of another configuration of the titanium package according to the present invention.
- FIG. 7 is a cross-sectional microstructure photograph of a Ti-0.1% N plate.
- FIG. 1 is an explanatory diagram showing an example of the configuration of the titanium composite 1 according to the present invention.
- the titanium composite material 1 includes surface layer portions 2 and 3 and an inner layer portion 4.
- each layer will be described.
- an industrial pure titanium material having a chemical composition belonging to any of JIS 1-4 can be used.
- the surface layer portions 2 and 3 are: C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance It has a chemical composition of Ti and impurities.
- JIS types 1 to 4 are defined in JIS 4600: 2012.
- JIS class 1 is C: 0.08% or less, H: 0.013% or less, O: 0.15% or less, N: 0.03% or less, Fe: 0.20% or less, the balance of Ti and impurities
- JIS type 2 is C: 0.08% or less, H: 0.013% or less, O: 0.20% or less, N: 0.03% or less, Fe: 0.25% or less, the balance of Ti and impurities Having a composition.
- JIS class 3 means C: 0.08% or less, H: 0.014% or less, O: 0.30% or less, N: 0.05% or less, Fe: 0.30% or less, the balance of Ti and impurities Having a composition.
- JIS class 4 means C: 0.08% or less, H: 0.013% or less, O: 0.40% or less, N: 0.05% or less, Fe: 0.50% or less, the balance of Ti and impurities Having a composition.
- an ⁇ -type titanium alloy, an ⁇ + ⁇ -type titanium alloy, or a ⁇ -type titanium alloy can be used as the titanium alloy material forming the surface layer portions 2 and 3.
- Examples of the ⁇ -type titanium alloy include Ti-0.06% Pd, Ti-0.2Pd, Ti-0.02Pd-0.05Mm (where Mm represents Misch metal), Ti-0.5Ni. -0.05Ru, Ti-0.5Cu, Ti-1.0Cu, Ti-1.0Cu-0.5Nb, Ti-1.0Cu-1.0Sn-0.3Si-0.25Nb, Ti-0.5Al -0.45Si, Ti-0.9Al-0.35Si, Ti-3Al-2.5V, Ti-5Al-2.5Sn, Ti-6Al-2Sn-4Zr-2Mo, Ti-6Al-2.75Sn-4Zr -0.4Mo-0.45Si.
- Examples of ⁇ + ⁇ type titanium alloys include Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-7V, Ti-3Al-5V, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-6Al. -2Sn-4Zr-6Mo, Ti-1Fe-0.35O, Ti-1.5Fe-0.5O, Ti-5Al-1Fe, Ti-5Al-1Fe-0.3Si, Ti-5Al-2Fe, Ti-5Al -2Fe-0.3Si, Ti-5Al-2Fe-3Mo, Ti-4.5Al-2Fe-2V-3Mo, and the like.
- ⁇ -type titanium alloy for example, Ti-11.5Mo-6Zr-4.5Sn, Ti-8V-3Al-6Cr-4Mo-4Zr, Ti-10V-2Fe-3Mo, Ti-13V-11Cr-3Al Ti-15V-3Al-3Cr-3Sn, Ti-6.8Mo-4.5Fe-1.5Al, Ti-20V-4Al-1Sn, Ti-22V-4Al, and the like.
- the thickness of the surface layer portions 2 and 3 is preferably 40% or less per side with respect to the total thickness of the titanium composite 1, and more preferably 25% or less per side.
- the thickness of the inner layer portion 4 is increased, so that the mechanical property improving effect is improved.
- the surface layer portions 2 and 3 are too thin, when the titanium composite material 1 is processed, the surface layer portions 2 and 3 are cracked and the inner layer portion 4 appears on the surface, and the titanium compound in the inner layer portion 4 falls off, Surface cracks and edge cracks occur with the titanium compound appearing in Further, when a liquid such as water comes into contact with the liquid, the problem that the liquid enters the inner layer portion 4 occurs. For this reason, it is preferable that the thickness of the surface layer portions 2 and 3 is 0.1 mm or more.
- a titanium compound 42 is dispersed in titanium 41, and each constituent element (that is, carbon around a carbide, nitrogen around a nitride, or oxygen around an oxide) around the titanium compound. ) Are diffused (not shown), and have a void 43 that is greater than 0% and not more than 30% in terms of area ratio.
- (B-1) Chemical composition of the inner layer part 4
- JIS class 1 to JIS class 4 industrial pure titanium can be used. That is, as general impurities, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, and the balance It is an industrial pure titanium which is Ti.
- JIS 1 to 3 types of industrial pure titanium has sufficient workability, does not generate cracks, etc., and industrial pure titanium that forms the above-mentioned surface portions 2 and 3 after hot working. And the titanium composite material 1 integrated.
- impurities As an impurity, it can contain in the range which does not reduce processability and a mechanical characteristic improvement effect. Impurities other than the above include Al, V, Cr, Nb, Si, Sn, Mo, Cu, and the like as impurity elements mainly mixed from scrap, and general impurity elements (C, N, Fe, O, H, etc.) In addition, a total amount of 5% or less is allowed.
- the inner layer portion 4 is made of a material in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium in order to make the titanium composite 1 have good mechanical properties.
- the total of the average contents of carbon, nitrogen and oxygen is preferably 0.05 to 2.0% by mass. The preferable range of the average content of each element and the reason for limitation will be described.
- the average concentration of C in the inner layer portion 4 is preferably 0.001 to 0.1%.
- the average concentration of N in the inner layer portion 4 is preferably 0.001 to 0.5%.
- the average concentration of O in the inner layer portion 4 is preferably 0.01 to 1.0%.
- Component analysis of the surface layer portion and the inner layer portion 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)).
- measurement is performed after cutting out the surface layer portion and the inner layer portion from the titanium composite material. It is efficient to collect and analyze an analysis sample from a chip obtained by machining the surface layer portion and the inner layer portion from the remaining material after the surface layer is deleted.
- As an analysis sample 0.5 g or more is collected from the center portion in the thickness direction of the surface layer portion and the inner layer portion.
- the surface layer or inner layer is thin and a sufficient amount of chips cannot be obtained, analyze the entire composition of the titanium composite and its analysis value and either the surface layer or inner layer analysis value And the component of the surface layer or the inner layer part may be calculated (reverse calculation) from each plate thickness.
- the voids 43 are contained to such an extent that the mechanical properties (strength, ductility, etc.) sufficient to maintain the structure as the titanium composite material 1 are contained, the density of the inner layer portion 4 becomes low, and the titanium composite The weight of the material 1 can be reduced.
- the porosity can be selected according to the application.
- the range of the porosity is preferably more than 0% and 30% or less, more preferably more than 0% and 10% or less.
- the porosity it is possible to have mechanical characteristics comparable to general industrial pure titanium.
- the ratio (void ratio) of the voids 43 remaining in the inner layer portion 4 of the titanium composite material 1 is calculated as follows. After embedding in the resin so that a cross section with a thickness parallel to the length direction (rolling direction) of the titanium composite material 1 can be observed, the observation surface is polished with a diamond or alumina suspension (mirror finish) and observed. Finish the sample.
- the observation sample that has been subjected to the mirror finish is photographed at 20 thickness centers at different positions with an optical microscope.
- the center portion is the thickness center when the titanium composite material 1 is a plate, and the center of the circular cross section when the titanium composite material 1 is a round bar.
- the area ratio of the voids 43 observed in the optical micrograph is measured, and the result of averaging the porosity values of the 20 photographs is calculated as the void ratio.
- a suitable magnification is selected according to the magnitude
- the porosity is 1% or less, since the void is small, it is preferable to take a picture while observing at a high magnification of about 500 times.
- the porosity is 10% or more, there are many large voids, so it is preferable to perform photography at a low magnification of about 20 times.
- the void ratio is 1% or less so that the voids become small, it is possible to observe more clearly than a normal optical microscope by using a differential interference microscope capable of observing polarized light.
- the inner layer part 4 in the titanium composite 1 contains a large amount of the titanium compound 42.
- the titanium compound 42 is made of each constituent element (that is, carbon around the carbide, nitrogen around the nitride, nitrogen, or oxide) around the titanium compound 42 by hot working or the like in the manufacturing process of the titanium composite 1.
- Each constituent element that cannot be dissolved in the titanium 41 remains as a titanium compound 42 in a dispersed state in the titanium material 41.
- the titanium compound 42 is aligned in the processing (rolling) direction and constitutes a streak-like compound aggregate 42a.
- the titanium compound 42 includes a compound in which carbon is present in addition to a compound that completely forms a compound. For example, when carbon is used as a material for a titanium compound, carbon reacts with titanium in a manufacturing process such as hot rolling to form a titanium compound, but the carbon that has not reacted with titanium inside the titanium compound. May remain.
- FIG. 2 is a diagram schematically showing the streak compound aggregate 42a.
- the streak-like compound aggregate 42a has a plurality of distances D (hereinafter referred to as “inter-particle distances”) obtained by projecting the distance between the centers of the grains of the titanium compound 42 in the rolling direction to 20 ⁇ m or less.
- An aggregate of titanium compounds 42 is meant. In the present specification, when the interparticle distance exceeds 20 ⁇ m, it is treated as another streak compound aggregate.
- the thickness t (that is, the size in the compression processing direction) of the streak compound aggregate 42a is 100 ⁇ m or less. This is because when the thickness exceeds 100 ⁇ m, the possibility of cracking starting from the titanium compound 42 increases when the titanium composite material is processed.
- the length L (that is, the size in the processing direction) of the streak compound aggregate 42a is 2.0 times or more the thickness (the thickness) t in the thickness direction (that is, L / t ⁇ 2). 0.0), more preferably 3.0 times or more (that is, L / t ⁇ 3.0). This is because when the length L is small, the inner layer portion is likely to be broken starting from this titanium compound when subjected to tensile stress. Note that L / t ⁇ 100 is preferable, and L / t ⁇ 40 is more preferable.
- the size (length L and thickness t) of the streak-like compound aggregate 42a is calculated as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation.
- the thickness center portion is the plate thickness center portion when the titanium composite material 1 is a plate, and is the center of the circular cross section when the titanium composite material 1 is a round bar.
- the length L and the thickness t of the streak-like compound aggregate 42a are measured, and the average value of each value is taken as the length L and the thickness t, and L / t is calculated.
- each constituent element that is, carbon for carbide, nitrogen for nitride, oxygen for oxide
- the diffusion layer is a titanium compound 42 dispersed in titanium 41 in the inner layer portion 4, and its constituent elements (carbon, nitrogen or oxygen) diffuse into the surrounding titanium 41 with the titanium compound 42 as the center, and a concentration gradient is formed. Refers to the layer.
- FIG. 3 shows a concept of the distance in the thickness direction of one grain and the concentration distribution of constituent elements around it in a cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite material 1.
- FIG. 3 When the diffusion layer is heated and held in the process of manufacturing the titanium composite material 1 (heating before hot rolling, during hot rolling, heat treatment after hot rolling, etc.), This is a layer formed by diffusing each constituent element in titanium 41. As shown in FIG. 3, the diffusion layer is contained in a larger amount than the value of each constituent element contained in the titanium 41 of the inner layer part 4. Due to the presence of this diffusion layer, the grains of the titanium compound 42 in the inner layer portion 4 and the titanium 41 are firmly bonded. For this reason, when the titanium composite material 1 is processed, the titanium compound 42 does not break from the starting point.
- This diffusion layer can be grasped as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation. Using EPMA, line analysis is performed in the thickness direction so that the grain of the titanium compound 42 observed in the observation sample is centered.
- the object of analysis is each constituent element (that is, carbon in the case of carbide, nitrogen in the case of nitride, oxygen in the case of oxide).
- a region having a higher concentration than the value of titanium 41 in the inner layer portion 4 and excluding particles is a diffusion layer.
- the thickness of the diffusion layer varies depending on various factors. For example, when a titanium compound is added, since it is formed by (1) decomposition of the titanium compound and (2) diffusion of each constituent element to the periphery, the decomposition rate of the titanium compound and the titanium material of each constituent element Varies depending on the diffusion rate. It also varies depending on the thermal history during manufacture. Furthermore, it changes also with the contact degree of sponge titanium etc. and a titanium compound at the time of the heating of the package as a hot rolling raw material. Therefore, the thickness of the diffusion layer has various diffusion layer thicknesses within the same material, and it is difficult to uniquely determine, but the titanium compound and each constituent element exist or exist. It is formed not a little around the part.
- (B-4) Thickness of the inner layer portion 4 As the thickness of the inner layer portion 4 with respect to the total thickness of the titanium composite material 1 increases, the mechanical characteristics improve. % Is preferable, and more preferably 50%. On the other hand, if the thickness is too large, the workability deteriorates. Therefore, the thickness of the inner layer portion 4 is preferably 95% or less with respect to the total thickness of the titanium composite material 1.
- Titanium packing body 5 includes a titanium packing material 6 and fillers 7 and 8.
- the shape of the titanium package 5 is not limited to a specific shape, but is determined by the shape of the titanium composite material 1 to be manufactured.
- a rectangular parallelepiped titanium package 5 is used.
- a cylindrical packing or a polygonal column shape titanium packing 5 such as an octagonal column is used.
- the size of the titanium package 5 is determined by the product size (thickness, width and length) and the production amount (mass).
- Titanium packing material 6 (A) Titanium packing material 6 (A-1) Titanium Packing Material 6 Chemical Composition
- the titanium packing material 6 is made of industrial pure titanium or titanium alloy material belonging to JIS class 1 to JIS class 4, similar to the surface layers 2 and 3 of the titanium composite material 1.
- Titanium packing material 6 shape Since the shape of the titanium packing material 6 depends on the shape of the titanium packing body 5 used as a material for hot working, there is no particular shape, and a plate material, a pipe material, or the like can be used. it can.
- the thickness of the titanium packing material 6 Is important.
- the thickness of the titanium packing material 6 is as thin as less than 1 mm, the titanium packing material 6 is broken in the course of hot working along with plastic deformation, and a part of the titanium packing body 5 falls off. In this case, the vacuum is broken at the same time, and the titanium material 7 filled in the titanium package 5 is oxidized. Further, the undulations of the titanium material 7 filled in the titanium package 5 are transferred to the surface of the titanium package 5, and there is a possibility that a large surface undulation may occur during hot working.
- the manufactured titanium composite material 1 deteriorates mechanical properties such as surface properties or ductility. Furthermore, when the titanium packing material 6 becomes too thin, there is a possibility that the weight of the titanium material 7 filled therein cannot be supported. For this reason, there exists a possibility that the rigidity of the titanium package 5 may be insufficient and deform during room temperature, hot holding or processing.
- the thickness of the titanium packing material 6 is , Preferably it is 1 mm or more, More preferably, it is 2 mm or more.
- the thickness of the titanium packing material 6 is preferably 25% or less of the total thickness of the titanium packing body 5. If the thickness of the titanium packing material 6 is greater than 25% of the total thickness of the titanium packing body 5, there is no particular problem in manufacturing, but the ratio of the titanium packing material 6 to the total thickness of the titanium packing body 5 is It becomes large and the thickness of the inside or the inner layer part 4 becomes thin. For this reason, the amount of the titanium compound in the titanium package 5 is reduced, and the effect of improving the mechanical properties is lowered, which is not preferable.
- Titanium material 7 The titanium material 7 as the filler is at least one selected from sponge titanium, titanium briquette and titanium scrap.
- (B-1-1) Chemical Composition of Titanium Material 7
- industrially pure titanium corresponding to JIS class 1 to JIS class 4 can be used. That is, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance Ti and the chemical composition of impurities Have.
- (B-1-2) Shape of Titanium Material 7 As the titanium material 7, normal sponge titanium produced by a refining process such as a conventional crawl method can be used.
- the size is preferably 20 mm or less in terms of average particle size.
- the average particle size is larger than 20 mm, it is difficult to uniformly mix with the powder 8 such as a titanium compound, and there is a possibility that unevenness of the titanium compound occurs in the inner layer portion 4 of the titanium composite 1 manufactured by hot working.
- the average particle size is small, there is no problem in terms of characteristics, but if the average particle size of the titanium material 7 is less than 0.5 mm, it takes time to crush and a lot of fine dust is scattered. Therefore, the production efficiency is deteriorated. For this reason, it is preferable that the average particle diameter of a titanium material is 0.5 mm or more.
- titanium scrap can be used as the titanium material 7.
- titanium scrap is used as a scrap that does not become a product generated in the manufacturing process of industrial pure titanium material, titanium chips generated when cutting and grinding to make industrial pure titanium material into a product shape, product It is a pure titanium material for industrial use that has become unnecessary after the processing. If the titanium scrap is too large, there is a problem that it is difficult to convey and difficult to put in the titanium package 5.
- sponge titanium or titanium scrap is in a lump shape, there is a gap (gap) 9 between the materials.
- powder 8 such as sponge titanium and titanium compound is mixed in advance and then compression molded to form briquette 10 as shown in FIG. You may put in.
- Powder of titanium compound or the like 8 (B-2-1) Chemical composition of powder 8 such as titanium compound
- the powder 8 such as titanium compound include carbon powder and TiC powder in the case of carbide, and TiN powder in the case of nitride. Fe 3 N powder, Fe 4 N powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 should not exceed the JIS standard) are exemplified. In the case of an oxide, TiO powder, TiO 2 powder, Ti 2 O In addition to the three powders, FeO powder, Fe 2 O 3 powder, Fe 3 O 4 powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 must not exceed the JIS standard) are exemplified. What is necessary is just to use what is marketed for these powders 8.
- the average particle diameter of the powder 8 such as a titanium compound exceeds 50 ⁇ m, it is difficult to uniformly mix with the titanium material 7. Therefore, the titanium compound cannot be uniformly dispersed in the inner layer portion 4 of the titanium composite material 1. For this reason, the average particle diameter of the powder 8 such as a titanium compound is preferably 50 ⁇ m or less.
- the average particle size of the powder 8 such as a titanium compound is smaller, there is no problem in terms of characteristics, but if it is too small, when mixing with the titanium material 7 or filling in the titanium package 5, There is a risk that the scattering of dust may cause problems. For this reason, it is preferable that the average particle diameter of the powder 8 such as a titanium compound is 0.1 ⁇ m or more.
- the internal pressure (absolute pressure) of the titanium package 5 should be 10 Pa or less, preferably 1 Pa or less.
- the internal pressure of the titanium package 5 is greater than 10 Pa, the titanium material 7 is oxidized or nitrided by the remaining air.
- Making the internal pressure extremely small requires improvement of the airtightness of the device and enhancement of the vacuum exhaust device, etc., leading to an increase in manufacturing cost. Therefore, the lower limit of the internal pressure is set to 1 ⁇ 10 ⁇ 3 Pa. Is good.
- the titanium composite material 1 is produced by subjecting the titanium package 5 to hot working or further cold working.
- the hot working method can be selected according to the shape of the product.
- the rectangular parallelepiped (slab) titanium package 5 is heated and hot-rolled to obtain a titanium plate. If necessary, after the hot rolling, the surface oxide layer may be removed by pickling or the like after hot rolling, and then cold rolling may be performed to further reduce the thickness.
- the cylindrical packing or polygonal (billet) titanium packing body 5 is heated and hot rolled or hot extruded to obtain a titanium round bar or wire.
- the oxide layer may be removed by pickling or the like, and then cold-rolled and further thinned as in the conventional process.
- (A-1) Heating temperature for hot working Further, when manufacturing the extruded titanium composite material 1, the cylindrical packing or polygonal (billet) titanium package 5 is heated to perform hot extrusion. Titanium profiles with various cross-sectional shapes are used. The heating temperature before hot working may be the same as that used when hot working a normal titanium slab or billet. The heating temperature varies depending on the size of the titanium package 5 and the degree of hot working (working rate), but it is preferable to heat to 600 ° C. or more and 1200 ° C. or less.
- the heating temperature is too low, the high temperature strength of the titanium package 5 is high and the deformability is low, so that cracking is likely to occur during hot working.
- the welded portion of the titanium package 5 is cracked and the inside is exposed and partly falls off or the inside is oxidized, the characteristics necessary for the titanium composite 1 cannot be obtained.
- the diffusion layer of the constituent elements around the titanium compound grains is not formed, and the titanium compound grains and titanium in the inner layer portion cannot be sufficiently bonded. For this reason, when processing a titanium composite material, a crack may generate
- the heating temperature is too high, the structure of the obtained titanium composite 1 becomes rough, and sufficient material properties cannot be obtained. Further, the packing material 6 on the surface is thinned by oxidation. Therefore, it is recommended that the heating temperature be 600 ° C. to 1200 ° C.
- the degree of hot working ie, the working rate, can be selected to control the porosity of the inner layer portion 4 of the titanium composite 1.
- the processing rate here is a ratio (percentage) obtained by dividing the difference between the cross-sectional area of the titanium package 5 and the cross-sectional area of the titanium composite 1 after hot working by the cross-sectional area of the titanium package 5.
- the gap 43 inside the titanium package 5 is not sufficiently crimped, so that the gap 43 remains even after hot working.
- the titanium composite material 1 containing a large amount of voids is lighter by the amount of voids contained, and there is no problem in the effect of improving mechanical properties.
- the processing rate is increased, the porosity is decreased and the mechanical properties are improved. For this reason, when the mechanical characteristics of the titanium composite material 1 to be manufactured are regarded as important, it is preferable that the processing rate is high.
- the titanium composite material 1 has no significant difference in the effect of improving the mechanical properties, whether it is a hot-worked material (for example, hot-rolled plate) or a cold-worked material (for example, cold-rolled plate). Further, the surface state may be any state of rolling, pickling finish and annealing finish, and the effect of improving mechanical properties is not changed.
- Manufacturing method of titanium package 5 (a) Mixing of fillers 7 and 8
- the titanium material 7 needs to be uniformly and densely filled with powder 8 such as a titanium compound.
- powder 8 such as a titanium compound.
- these titanium material 7 and titanium compound powder 8 are filled in a container and rotated or vibrated, and mixed so that the internal titanium material 7 and titanium compound powder 8 are uniformly dispersed. do it.
- Stirring can be done by rotating the container up and down, tilting it 20 to 70 ° from the horizontal and rotating it in an oblique direction, vibrating the container in the vertical and horizontal directions, or inserting a stirring bar into the container and stirring. Examples include a method of rotating the child.
- the stirring time varies depending on the size of the container and the amount of the titanium material 7 to be mixed and the powder 8 of the titanium compound or the like, but is preferably 1 to 30 minutes. In consideration of productivity, it is preferable to determine the size of the container and the processing amount so that the mixture can be uniformly mixed within a few minutes.
- the mixed titanium material 7 and powder 8 such as titanium compound are filled in the titanium package 5 as they are.
- the titanium briquette 10 as shown in FIG.
- the method of welding the titanium packing material 6 with the welded portion 11 includes arc welding such as TIG welding or MIG welding, electron beam welding, laser welding, and the like, and is not particularly limited. However, it is preferable that welding is performed in a vacuum atmosphere or an inert gas atmosphere so that the surfaces of the titanium material 7 and the titanium packing material 6 are not oxidized or nitrided.
- the titanium packing body 5 is put in a vacuum atmosphere container (chamber) and welded to keep the inside of the titanium packing body 5 in a vacuum. Is preferred.
- a titanium briquette 10 mixed with a powder 8 such as a titanium compound and compression-molded is covered with a titanium expanded material as a packing material, and the entire circumference of the titanium expanded material is seam welded (using a rotating electrode).
- the titanium package 12 may be manufactured by sealing with resistance welding.
- the inside of the titanium wrought material is depressurized to a predetermined pressure through a copper pipe in which a hole is drilled at the end in advance and the copper pipe is solder-welded. The pressure inside the material may be maintained.
- titanium composite 1 Since it has high tensile strength and good workability and can be manufactured at low cost, it can be used as a structural member for land transportation equipment such as automobiles.
- a titanium package shown in Table 1 was produced, and a titanium composite 1 (plate material) was produced in the production process shown in Table 1 on the titanium package.
- the particle size produced by the crawl method is 2.5 mm or more and 6 mm or less, and the chemical composition is equivalent to JIS class 1 (C: 0.002%, H: 0.001%, O: 0.03%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) were used.
- the filler commercially available TiO 2 powder (average particle size 2 ⁇ m), TiC powder (average particle size 3 ⁇ m) or TiN powder (average particle size 5 ⁇ m) was used.
- the above-mentioned sponge titanium and powders of titanium compound and the like were mixed by feeding a predetermined amount into a V-type mixer.
- the mixed material was put into a mold and compression molded to form a titanium briquette shown in FIG. 5 having a thickness of 15 mm, a width of 50 mm, and a length of 60 mm.
- Sample No. In No. 11 only titanium titanium particles 7 were added, and titanium briquette was prepared without adding the powder raw material 8.
- JIS type 1 As a titanium packing material, JIS type 1 (TP270C; C: 0.001%, H: 0.005%, O: 0.04%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) Or JIS type 2 (TP340C; C: 0.002%, H: 0.004%, O: 0.09%, N: 0.001%, Fe: 0.05%, balance Ti and impurities) industrial pure titanium A thin plate made of a material and having a thickness of 1.0 mm was used.
- the titanium briquette was covered with an industrial pure titanium material as a packing material, and the entire circumference of the industrial pure titanium material was sealed by seam welding (resistance welding using a rotating electrode).
- This pure titanium material for industrial use was previously welded to a copper tube by making a hole in the end.
- the pressure inside the industrial pure titanium material is reduced to a predetermined pressure (0.06 to 1.2 Pa) through the copper tube. The pressure was maintained.
- Sample No. 12 when the pressure was reduced to 38 Pa, a copper tube was pressure-bonded to form a package.
- the produced titanium package was heated at 850 ° C. for 4 hours in an air atmosphere and then hot-rolled to produce a 2.0 mm-thick titanium composite.
- the titanium composite was annealed at 725 ° C. for 15 minutes, then pickled to remove the scale of the surface layer, and subjected to a structure observation and a tensile test.
- the observation surface is polished with diamond or alumina suspension ( Mirror finish) and finished the sample for observation.
- the porosity was obtained by taking 20 photographs of the central portion of the thickness of the observation sample with an optical microscope, measuring the area ratio of the void for each individual photograph, and obtaining the average value thereof.
- the shape of the streak-like compound aggregate was determined by observing the central portion of the thickness of the observation sample with an optical microscope. Moreover, about 20 observed streak compound aggregates, thickness t and length L were measured, L / t was calculated, and those average values were calculated
- the thickness of the diffusion layer is No. 1 to which TiO 2 powder, TiC powder and TiN powder were added. 2, No. 4, no. As for No. 6, the five titanium compound grains observed in the central portion of the thickness of the observation sample were measured with EPMA for the three titanium compound grains observed therein. Perform line analysis in the thickness direction so that the grains of the titanium compound are in the center, and based on the value of titanium in the inner layer, the concentration of the constituent elements (carbon, nitrogen or oxygen) of the titanium compound is higher than that, The distance of the area
- the tensile test was evaluated in the rolling direction of the titanium composite material.
- the tensile rate was 0.4% / min until exceeding the yield point, and 30% / min after exceeding the yield point, and the strength was measured.
- the Young's modulus was obtained from the slope of the stress-strain curve until yielding.
- FIG. 7 is an example of a photograph of a cross-sectional microstructure of a Ti-0.1% N plate.
- Sample No. of the present invention example in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium. Samples Nos. 1 to 8 have no titanium compound. Compared to 10, the strength and Young's modulus of the titanium composite were improved. Note that when the titanium package 5 was manufactured, the sample No. 1 with the degree of vacuum inside the titanium package greater than 10 Pa was used. In No. 9, the inside of the titanium composite was partially oxidized and the strength decreased, but the Young's modulus was maintained at a certain value or more. No. with TiO 2 powder added. In No. 2, the thickness of the oxygen diffusion layer was 4 to 6 ⁇ m. No. to which TiC powder was added. In No. 4, the thickness of the carbon diffusion layer was 25 to 32 ⁇ m. No. with TiN powder added. In No. 6, the thickness of the nitrogen diffusion layer was 1-2 ⁇ m.
- Sample No. with a large amount of oxide powder added In No. 11, an internal crack occurred during hot rolling, and a healthy titanium composite material could not be obtained.
- the oxide was interspersed with the voids without directionality, and cracked when the tensile test piece was manufactured.
- a titanium composite material was manufactured from a titanium package.
- Sponge titanium used as a filler has a chemical composition produced by the crawl method equivalent to JIS class 1 (C: 0.001%, H: 0.001%, O: 0.04%, N: 0.001%, Fe : 0.03%, balance Ti and impurities), sponge titanium B has a particle size of 6 mm to 13 mm, sponge titanium C has a particle size of 2.5 mm to 6 mm, and sponge titanium D has a particle size of Each having a thickness of 0.8 mm to 2.5 mm.
- TiO 2 powder average particle size 2 ⁇ m
- TiC powder average particle size 3 ⁇ m
- TiN powder average particle size 5 ⁇ m
- industrial pure titanium material is JIS type 1 (TP270HC: 0.002%, H: 0.006%, O: 0.04%, N: 0.002%, Fe: 0.03%) , Balance Ti and impurities), JIS type 2 (TP340H; C: 0.001%, H: 0.002%, O: 0.10%, N: 0.002%, Fe: 0.06%, balance Ti and Impurities), and a 10 mm thick plate washed with Ti-0.06% Pd.
- a titanium packing body was prepared in which the inside was filled with a mixture of titanium sponge, titanium scrap, and a powder of a titanium compound, and the atmosphere was vacuum.
- the size of the titanium package was 80 x thickness 100 x length 120 mm.
- the produced titanium package was heated at 850 ° C. for 6 hours in an air atmosphere, and then hot-rolled to produce a titanium composite plate having a thickness of 5 mm. Thereafter, the titanium composite was annealed at 725 ° C. for 15 minutes, and then pickled to remove the scale of the surface layer and subjected to a tensile test.
- the structure observation and the tensile test were performed in the same manner as in Example 1, and the porosity of the titanium composite material, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer were determined.
- sample No. which is an example of the present invention to which titanium compound powder is added.
- Samples Nos. 13 to 19 are sample Nos. To which no titanium compound was added. Compared to 20, the strength and Young's modulus of the titanium composite were improved.
- the titanium composite material 1 with good workability is obtained as compared with the packaging material using JIS type 2.
- Sample No. 6 using Ti-0.06% Pd as the packing material 6 was used.
- No. 23 is a titanium composite material with better corrosion resistance than the packaging material 6 using JIS type 2.
- the thickness of the oxygen diffusion layer was 2 to 6 ⁇ m.
- the thickness of the carbon diffusion layer was 12 to 18 ⁇ m.
- the thickness of the nitrogen diffusion layer was 1-2 ⁇ m.
- Sample No. 5 which is a titanium composite material having a thickness of 5 mm shown in Table 2 obtained by hot rolling. 13, 14, 16, and 20 were annealed at 725 ° C. for 15 minutes, and then pickled to remove scale on the surface layer.
- the titanium composite from which the scale was removed (hot-rolled material) was cold-rolled to a thickness of 1.0 mm, and then annealed at 700 ° C. for 15 minutes using a vacuum heating furnace and subjected to a tensile test. Microstructure observation and a tensile test were performed in the same manner as in Example 1 to determine the porosity of the titanium composite, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer.
- Sample No. which is an example of the present invention Samples Nos. 28 to 30 were prepared by adding the titanium compound powder, so that no sample no. Compared to 31, the strength and Young's modulus of the titanium composite were improved. In addition, No. to which TiO 2 powder was added. In No. 29, the thickness of the oxygen diffusion layer was 1 to 4 ⁇ m. No. to which TiC powder was added. In No. 30, the thickness of the carbon diffusion layer was 2 to 6 ⁇ m.
Abstract
A titanium composite material 1 has an inner layer part 4 and outer layer parts 2, 3, the outer layer parts 2, 3 comprise titanium alloy or commercially pure titanium having a chemical composition belonging to any of JIS types 1 through 4, and the inner layer 4 is provided with a portion in which one or more types of titanium compounds selected from a carbide, a nitride, and an oxide are dispersed in titanium, carbon being diffused on the periphery of the carbide, nitrogen being diffused on the periphery of the nitride, and oxygen being diffused on the periphery of the oxide, and has voids in an area ratio of more than 0% to no more than 30%. The titanium composite material 1 has excellent mechanical characteristics and can be manufactured at low cost.
Description
本発明は、チタン複合材およびその製造方法、ならびに、梱包体に関する。
The present invention relates to a titanium composite material, a manufacturing method thereof, and a package.
チタン材は、耐食性に優れた金属材料であることから、海水を用いる熱交換器や各種の化学プラント等に用いられている。また、密度が炭素鋼に比べて小さく、比強度（単位重量あたりの強度）に優れることから、航空機の機体にも多く使用されている。また、自動車等の陸上輸送機器にチタン材を使用することにより、陸上輸送機器自体が軽量となり、燃費向上が期待される。
Titanium is a metal material with excellent corrosion resistance, and is used in heat exchangers using seawater, various chemical plants, and the like. Moreover, since the density is smaller than that of carbon steel and excellent in specific strength (strength per unit weight), it is often used in aircraft bodies. In addition, by using titanium material for land transportation equipment such as automobiles, the land transportation equipment itself is light and expected to improve fuel efficiency.
しかし、チタン材は、鋼材に比べて複雑で非常に多くの工程を経て製造される。代表的な製造工程を以下に例示する。
（１）製錬工程：原料である酸化チタンを塩素化して四塩化チタンとした後、マグネシウムあるいはナトリウムで還元することにより、海綿状（塊状）の金属チタン（以下、「スポンジチタン」という）を製造する工程
（２）溶解工程：スポンジチタンをプレス成形して電極とし、真空アーク溶解炉で溶解して鋳塊を製造する工程
（３）鍛造工程：鋳塊を熱間で鍛造してスラブ（熱間圧延素材）やビレット（熱間押出しや熱間圧延などの素材）などを製造する工程
（４）熱間加工工程：スラブやビレットを加熱して熱間で圧延や押出しして板や丸棒などを製造する工程
（５）冷間加工工程：板や丸棒をさらに冷間で圧延加工や押出しして薄板や丸棒、線などを製造する工程 However, titanium materials are more complicated than steel materials and are manufactured through many processes. A typical manufacturing process is illustrated below.
(1) Smelting process: Titanium oxide as a raw material is chlorinated to titanium tetrachloride, and then reduced with magnesium or sodium to form sponge-like (lumped) metal titanium (hereinafter referred to as “sponge titanium”). Manufacturing process (2) Melting process: Titanium sponge is press-molded to form an electrode and melted in a vacuum arc melting furnace to produce an ingot. (3) Forging process: The ingot is hot forged into a slab ( (4) Hot working process: A slab or billet is heated and rolled or extruded hot to produce a plate or a round shape (hot rolled material) or billet (material such as hot extrusion or hot rolling) Steps for manufacturing bars, etc. (5) Cold working step: Steps for producing thin plates, round bars, wires, etc. by further cold rolling and extruding plates and round bars.
（１）製錬工程：原料である酸化チタンを塩素化して四塩化チタンとした後、マグネシウムあるいはナトリウムで還元することにより、海綿状（塊状）の金属チタン（以下、「スポンジチタン」という）を製造する工程
（２）溶解工程：スポンジチタンをプレス成形して電極とし、真空アーク溶解炉で溶解して鋳塊を製造する工程
（３）鍛造工程：鋳塊を熱間で鍛造してスラブ（熱間圧延素材）やビレット（熱間押出しや熱間圧延などの素材）などを製造する工程
（４）熱間加工工程：スラブやビレットを加熱して熱間で圧延や押出しして板や丸棒などを製造する工程
（５）冷間加工工程：板や丸棒をさらに冷間で圧延加工や押出しして薄板や丸棒、線などを製造する工程 However, titanium materials are more complicated than steel materials and are manufactured through many processes. A typical manufacturing process is illustrated below.
(1) Smelting process: Titanium oxide as a raw material is chlorinated to titanium tetrachloride, and then reduced with magnesium or sodium to form sponge-like (lumped) metal titanium (hereinafter referred to as “sponge titanium”). Manufacturing process (2) Melting process: Titanium sponge is press-molded to form an electrode and melted in a vacuum arc melting furnace to produce an ingot. (3) Forging process: The ingot is hot forged into a slab ( (4) Hot working process: A slab or billet is heated and rolled or extruded hot to produce a plate or a round shape (hot rolled material) or billet (material such as hot extrusion or hot rolling) Steps for manufacturing bars, etc. (5) Cold working step: Steps for producing thin plates, round bars, wires, etc. by further cold rolling and extruding plates and round bars.
チタン材は、このように多くの工程により製造されるため、非常に高価である。このため、チタン材は自動車等の陸上輸送機器には殆ど適用されていない。このため、チタン材の利用を促進するためには、その製造工程の生産性を高める必要がある。この課題に対処するため、チタン材の製造工程を簡略化する取り組みがなされている。
Titanium material is very expensive because it is manufactured in many processes. For this reason, titanium materials are hardly applied to land transportation equipment such as automobiles. For this reason, in order to promote utilization of the titanium material, it is necessary to increase the productivity of the manufacturing process. In order to cope with this problem, efforts have been made to simplify the manufacturing process of the titanium material.
特許文献１には、チタン粉、結着剤、可塑剤、溶剤を含む組成物を薄板状に成形、乾燥、焼結、圧密および再焼結してチタン薄板を製造する方法が開示されている。この方法によれば、上記溶解工程、鍛造工程、熱間圧延工程および冷間圧延工程を省略できる。
Patent Document 1 discloses a method for producing a titanium thin plate by forming a composition containing titanium powder, a binder, a plasticizer, and a solvent into a thin plate shape, drying, sintering, compacting, and re-sintering. . According to this method, the melting step, the forging step, the hot rolling step, and the cold rolling step can be omitted.
特許文献２には、チタン合金粉に銅粉、クロム粉または鉄粉を添加して、炭素鋼製のカプセルに封入し、加熱して熱間で押出ししてチタン合金丸棒を製造する方法が開示されている。この方法によれば、上記溶解工程および鍛造工程を省略できるため、製造コストを下げることができる。
Patent Document 2 discloses a method of manufacturing a titanium alloy round bar by adding copper powder, chromium powder or iron powder to titanium alloy powder, enclosing it in a carbon steel capsule, heating and extruding it hot. It is disclosed. According to this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
特許文献３には、スポンジチタン粉を銅製カプセルに充填して、７００℃以下に加熱して温間押出し加工を施して、丸棒を製造する方法が開示されている。この方法では、上記溶解工程および鍛造工程を省略できるため、製造コストを下げることができる。
Patent Document 3 discloses a method of manufacturing a round bar by filling sponge titanium powder in a copper capsule, heating to 700 ° C. or lower, and performing a warm extrusion process. In this method, since the melting step and the forging step can be omitted, the manufacturing cost can be reduced.
また、従来から知られているパック圧延は、加工性の悪いチタン合金などのコア材を加工性の良い安価な炭素鋼などのカバー材で被覆して熱間圧延する方法である。例えば、コア材の表面に剥離剤を塗布した後、少なくともその上下２面をカバー材で被覆、あるいは上下面の他に４周面もカバー材で被覆して、合わせ目を溶接して密閉被覆箱を製作し、その内部を真空に引いて密閉してから熱間圧延する。
Further, conventionally known pack rolling is a method in which a core material such as a titanium alloy having poor workability is covered with a cover material such as inexpensive carbon steel having good workability and hot rolling is performed. For example, after the release agent is applied to the surface of the core material, at least two upper and lower surfaces thereof are covered with a cover material, or in addition to the upper and lower surfaces, four peripheral surfaces are also covered with a cover material, and a seam is welded and hermetically covered A box is manufactured, the inside of which is evacuated and sealed, and then hot rolled.
パック圧延に関して、特許文献４には、密閉被覆箱の組立方法が開示され、特許文献５には、１０－３ｔｏｒｒ（約０．１３３Ｐａ）以上の真空度にしてカバー材を密封（パック）して密閉被覆箱を製造する方法が開示され、さらに、特許文献６には、炭素鋼（カバー材）で覆って、１０－２ｔｏｒｒ（約１．３３Ｐａ）以下の真空下で高エネルギー密度溶接によって密封（パック）して、密閉被覆箱を製造する方法が開示されている。
With regard to pack rolling, Patent Document 4 discloses a method for assembling a hermetically sealed box, and Patent Document 5 discloses that a cover material is sealed (packed) at a vacuum degree of 10 −3 torr (about 0.133 Pa) or more. Further, a method for producing a hermetically sealed box is disclosed. Further, Patent Document 6 covers carbon steel (cover material) and performs high energy density welding under a vacuum of 10 −2 torr (about 1.33 Pa) or less. A method for producing a hermetically sealed box by sealing (packing) is disclosed.
これらのパック圧延では、被圧延材であるコア材をカバー材で覆って熱間圧延するため、コア材の表面は冷えた媒体（大気やロール）に直接触れることがなく、コア材の温度低下を抑制できるため、加工性の悪いコア材でも薄板の製造が可能になる。
In these pack rolling, the core material, which is the material to be rolled, is covered with a cover material and hot-rolled, so the surface of the core material does not come into direct contact with the cold medium (air or roll), and the temperature of the core material decreases. Therefore, even a core material with poor workability can be manufactured.
カバー材として、コア材と異なる材質で、加工性が良く安価な炭素鋼などを用いている。カバー材は熱間圧延後に不要となるため、コア材から分離し易くするために、コア材の表面には剥離剤が塗布される。
As the cover material, carbon steel, etc., which is different from the core material, has good workability and is inexpensive. Since the cover material becomes unnecessary after hot rolling, a release agent is applied to the surface of the core material in order to facilitate separation from the core material.
特許文献１により開示された方法では、高価なチタン粉（平均粒子径が４～２００μｍ）を原料として用いることや、焼結や圧密などの多くの工程が必要であるため、得られたチタン薄板は非常に高価であり、チタン材の利用促進には至っていない。
In the method disclosed in Patent Document 1, an expensive titanium powder (average particle size of 4 to 200 μm) is used as a raw material, and many processes such as sintering and compaction are required. Is very expensive and has not yet promoted the use of titanium.
特許文献２により開示された方法では、高価なチタン粉合金を原料として使用するため、得られたチタン合金丸棒は高価であり、チタン材の利用促進には至っていない。しかも、加熱した際にスポンジチタン粉が酸化されるため、得られた丸棒は表層や内部に酸化チタンを含み、通常工程で製造した丸棒に比べて、外観が変色し、引張特性が劣る等の問題がある。
In the method disclosed in Patent Document 2, since an expensive titanium powder alloy is used as a raw material, the obtained titanium alloy round bar is expensive, and the use of titanium material has not been promoted. Moreover, since the titanium sponge powder is oxidized when heated, the obtained round bar contains titanium oxide in the surface layer and inside, and the appearance changes in color and the tensile properties are inferior compared to the round bar produced in the normal process. There are problems such as.
特許文献３により開示された方法では、加熱した際にスポンジチタン粉が酸化されるため、得られる丸棒は表層および内部に酸化チタンを含み、通常工程で製造した丸棒に比べて、外観が変色し、引張特性が劣る等の問題がある。
In the method disclosed in Patent Document 3, since the sponge titanium powder is oxidized when heated, the resulting round bar contains titanium oxide in the surface layer and the inside, and the appearance is larger than that of a round bar manufactured in a normal process. There are problems such as discoloration and poor tensile properties.
さらに、特許文献４～６により開示された方法は、パック圧延のように圧延後にカバー材を剥がして廃却するため、製造コストが通常の工程よりも高くなり、得られたチタン材は、高コストであることに変わりがない。
Furthermore, since the methods disclosed in Patent Documents 4 to 6 are stripped and discarded after rolling as in pack rolling, the manufacturing cost is higher than that in a normal process, and the obtained titanium material has a high The cost remains the same.
このため、チタン材は、自動車などの陸上輸送機器に適用されるまでには至っていない。
For this reason, titanium materials have not yet been applied to land transportation equipment such as automobiles.
本発明は、このような実情に鑑み、低コストでチタン板やチタン丸棒などのチタン材を提供することを目的とする。
In view of such circumstances, an object of the present invention is to provide a titanium material such as a titanium plate or a titanium round bar at a low cost.
本発明者らは、上記課題を解決するために溶解工程と鍛造工程を省略してチタン材を製造できる手段を鋭意検討し、以下に列記の知見（Ａ）～（Ｆ）を得て、本発明を完成した。
In order to solve the above-mentioned problems, the present inventors diligently studied means for producing a titanium material by omitting the melting step and the forging step, and obtained the knowledge (A) to (F) listed below. Completed the invention.
（Ａ）高価なチタン粉やスポンジチタン粉のような粉末ではなく、不定形で海綿状（塊状）のスポンジチタンを原料として使用する。海綿状のスポンジチタンは、従来から製造されているため、比較的安価に入手できる。また、スポンジチタンは製錬工程において鉄や塩素等の主な不純物が除去されているため、スポンジチタンからチタン材を直接製造しても、化学組成上の問題はない。また、製品にはならない端材等のチタン材（以下、「チタンスクラップ」という。）は、比較的安価に入手することができる。ただし、チタンスクラップは不定形であるため、直接加工してチタン材を製造することはできない。
(A) Instead of powder such as expensive titanium powder or sponge titanium powder, amorphous and sponge-like (lumped) sponge titanium is used as a raw material. Since sponge-like sponge titanium has been conventionally produced, it can be obtained at a relatively low cost. In addition, since titanium sponge has main impurities such as iron and chlorine removed in the smelting process, there is no problem in chemical composition even if a titanium material is directly produced from sponge titanium. Moreover, titanium materials (hereinafter referred to as “titanium scrap”) such as mill ends that cannot be manufactured can be obtained at a relatively low cost. However, since titanium scrap is indefinite, it cannot be directly processed to produce a titanium material.
（Ｂ）工業用純チタン材やチタン合金材を用いて作製した容器（以下、「梱包材」という。）に、スポンジチタンなどの充填材を収容して密閉したチタン梱包体であれば、熱間加工した際に、表面割れやヘゲ状等の表面欠陥の発生を抑制できる。特に、充填材の化学組成を純チタン材と同種のものにすることによって、従来のパック圧延のように圧延後にカバー材を剥がして廃却する必要はなく、チタン梱包材を、熱間加工後にもそのままチタン複合材（製品）の一部として有効に利用できる。
(B) If it is a titanium package that contains a filler such as sponge titanium in a container (hereinafter referred to as “packaging material”) manufactured using a pure industrial titanium material or a titanium alloy material, Generation of surface defects such as surface cracks and shavings can be suppressed during the hot working. In particular, by making the chemical composition of the filler the same type as that of pure titanium material, it is not necessary to peel off and discard the cover material after rolling as in conventional pack rolling. Can also be used effectively as part of a titanium composite (product).
（Ｃ）熱間加工前に加熱した際に、スポンジチタンなどの充填材が酸化しないように、また、熱間加工時に充填材間や充填材と梱包材の間にある空隙が減少し易いように、梱包材の内圧を極力減圧しておくことが重要である。
(C) When heated before hot working, fillers such as sponge titanium are not oxidized, and gaps between fillers and between fillers and packing materials are likely to be reduced during hot working. In addition, it is important to reduce the internal pressure of the packing material as much as possible.
（Ｄ）梱包材に収容する充填材として、スポンジチタンなどのチタン材とともに、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末を充填することにより、チタン複合材の引張強度を高めることができる。
(D) Tensile strength of titanium composite material by filling one or more powders selected from carbon, carbide, nitride and oxide with a titanium material such as sponge titanium as a filler to be contained in the packing material Can be increased.
（Ｅ）すなわち、工業用純チタンの展伸材であるチタン梱包材の内部に、スポンジチタンと、チタン複合材の引張強度を高めることができる炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末とを充填および封入し、内部を減圧してチタン梱包体とし、このチタン梱包体に熱間加工を行い、必要に応じてさらに冷間加工も行ってチタン複合材とすることにより、熱間加工前にはチタン塊の集合であったチタン梱包体が、熱間加工後には全体として圧縮成形されて一体化したチタン複合材（三層のクラッド材）となる。
(E) That is, selected from carbon, carbide, nitride, and oxide that can increase the tensile strength of titanium sponge and titanium composite material in the titanium packing material that is an expanded material of industrial pure titanium Fill and enclose one or more powders, depressurize the inside to form a titanium package, perform hot working on this titanium package, and further cold work as necessary to obtain a titanium composite. Thus, the titanium package, which is a collection of titanium ingots before hot working, becomes a titanium composite material (three-layer clad material) that is compressed and integrated as a whole after hot working.
（Ｆ）チタン複合材は、内層部のみがチタン複合材の引張強度を高めることができる炭化物、窒化物および酸化物から選択される１種以上のチタン化合物を含有するチタンの圧縮成形体であるが、表層部は工業用純チタンまたはチタン合金材の展伸材であるため、優れた加工性と高い引張強度を有するとともに、従来の溶解工程や鍛造工程を経ずに製造できるために製造コストを大幅に低減できる。
(F) The titanium composite is a compression-molded body of titanium containing only one or more titanium compounds selected from carbides, nitrides and oxides whose only inner layer portion can increase the tensile strength of the titanium composite. However, since the surface layer is a wrought material of industrial pure titanium or titanium alloy material, it has excellent workability and high tensile strength, and can be manufactured without the conventional melting process and forging process. Can be greatly reduced.
本発明は、以下に列記の通りである。
The present invention is as listed below.
（１）内層部と前記内層部を覆う表層部とを有するチタン複合材であって、
前記表層部は、ＪＩＳ１種～４種のいずれかに属する化学組成の工業用純チタン材またはチタン合金材からなり、
前記内層部は、チタンに、炭化物、窒化物および酸化物から選択される１種以上のチタン化合物が分散しており、前記炭化物の周囲に炭素が、前記窒化物の周囲に窒素が、前記酸化物の周囲に酸素が、それぞれが拡散した部分を備え、面積率で、０％超３０％以下の空隙を有する、
チタン複合材。 (1) A titanium composite material having an inner layer portion and a surface layer portion covering the inner layer portion,
The surface layer portion is made of an industrial pure titanium material or a titanium alloy material having a chemical composition belonging to any one ofJIS types 1 to 4,
In the inner layer portion, one or more kinds of titanium compounds selected from carbide, nitride and oxide are dispersed in titanium, carbon around the carbide, nitrogen around the nitride, and the oxidation Oxygen around each object has a portion where each diffuses, and the area ratio has voids of more than 0% and not more than 30%.
Titanium composite.
前記表層部は、ＪＩＳ１種～４種のいずれかに属する化学組成の工業用純チタン材またはチタン合金材からなり、
前記内層部は、チタンに、炭化物、窒化物および酸化物から選択される１種以上のチタン化合物が分散しており、前記炭化物の周囲に炭素が、前記窒化物の周囲に窒素が、前記酸化物の周囲に酸素が、それぞれが拡散した部分を備え、面積率で、０％超３０％以下の空隙を有する、
チタン複合材。 (1) A titanium composite material having an inner layer portion and a surface layer portion covering the inner layer portion,
The surface layer portion is made of an industrial pure titanium material or a titanium alloy material having a chemical composition belonging to any one of
In the inner layer portion, one or more kinds of titanium compounds selected from carbide, nitride and oxide are dispersed in titanium, carbon around the carbide, nitrogen around the nitride, and the oxidation Oxygen around each object has a portion where each diffuses, and the area ratio has voids of more than 0% and not more than 30%.
Titanium composite.
（２）前記内層部は、炭素、窒素および酸素の平均含有量の合計が０．０５～２．０質量％であり、前記チタン化合物が圧延方向に並んだ筋状化合物集合体としてチタン材に分散している、
上記（１）のチタン複合材。 (2) The inner layer portion has a total content of carbon, nitrogen and oxygen of 0.05 to 2.0% by mass, and the titanium compound is formed into a titanium material as a streak compound aggregate in which the titanium compounds are arranged in the rolling direction. Decentralized,
The titanium composite material of (1) above.
上記（１）のチタン複合材。 (2) The inner layer portion has a total content of carbon, nitrogen and oxygen of 0.05 to 2.0% by mass, and the titanium compound is formed into a titanium material as a streak compound aggregate in which the titanium compounds are arranged in the rolling direction. Decentralized,
The titanium composite material of (1) above.
（３）前記工業用純チタン材の化学組成は、質量％で、
Ｃ：０．０８％以下、
Ｈ：０．０１３％以下、
Ｏ：０．４％以下、
Ｎ：０．０５％以下、
Ｆｅ：０．５％以下、
残部：Ｔｉおよび不純物である、
上記（１）または（２）のチタン複合材。 (3) The chemical composition of the industrial pure titanium material is mass%,
C: 0.08% or less,
H: 0.013% or less,
O: 0.4% or less,
N: 0.05% or less,
Fe: 0.5% or less,
Balance: Ti and impurities,
The titanium composite material according to (1) or (2) above.
Ｃ：０．０８％以下、
Ｈ：０．０１３％以下、
Ｏ：０．４％以下、
Ｎ：０．０５％以下、
Ｆｅ：０．５％以下、
残部：Ｔｉおよび不純物である、
上記（１）または（２）のチタン複合材。 (3) The chemical composition of the industrial pure titanium material is mass%,
C: 0.08% or less,
H: 0.013% or less,
O: 0.4% or less,
N: 0.05% or less,
Fe: 0.5% or less,
Balance: Ti and impurities,
The titanium composite material according to (1) or (2) above.
（４）ＪＩＳ１～４種のいずれかに属する工業用純チタン材またはチタン合金材からなるチタン梱包材に、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上と、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末と充填し、封入し、内部を１０Ｐａ以下に減圧することによりチタン梱包体とし、前記チタン梱包体に熱間加工を行う、
チタン複合材の製造方法。 (4) Titanium packing material made of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4, one or more selected from sponge titanium, titanium briquette and titanium scrap, and carbon, carbide, nitriding Filled with one or more powders selected from products and oxides, sealed, and reduced in pressure to 10 Pa or less inside to form a titanium package, and hot processing the titanium package,
A method for producing a titanium composite material.
チタン複合材の製造方法。 (4) Titanium packing material made of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4, one or more selected from sponge titanium, titanium briquette and titanium scrap, and carbon, carbide, nitriding Filled with one or more powders selected from products and oxides, sealed, and reduced in pressure to 10 Pa or less inside to form a titanium package, and hot processing the titanium package,
A method for producing a titanium composite material.
（５）前記熱間加工を行った後に冷間加工を行う、
上記（４）のチタン複合材の製造方法。 (5) Cold work is performed after the hot work is performed.
The manufacturing method of the titanium composite material of said (4).
上記（４）のチタン複合材の製造方法。 (5) Cold work is performed after the hot work is performed.
The manufacturing method of the titanium composite material of said (4).
（６）ＪＩＳ１～４種のいずれかに属する工業用純チタン材またはチタン合金材からなるチタン梱包材と、前記チタン梱包材の内部に充填された充填材とを備える梱包体であって、
前記充填材が、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上と、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末とを有し、前記内部の圧力は１０Ｐａ以下である、
熱間加工用の梱包体。 (6) A packing body comprising a titanium packing material made of an industrial pure titanium material or a titanium alloy material belonging to any one of JIS 1-4, and a filler filled in the titanium packing material,
The filler has at least one selected from sponge titanium, titanium briquette and titanium scrap, and at least one powder selected from carbon, carbide, nitride and oxide, and the internal pressure is 10 Pa or less,
Package for hot working.
前記充填材が、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上と、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末とを有し、前記内部の圧力は１０Ｐａ以下である、
熱間加工用の梱包体。 (6) A packing body comprising a titanium packing material made of an industrial pure titanium material or a titanium alloy material belonging to any one of JIS 1-4, and a filler filled in the titanium packing material,
The filler has at least one selected from sponge titanium, titanium briquette and titanium scrap, and at least one powder selected from carbon, carbide, nitride and oxide, and the internal pressure is 10 Pa or less,
Package for hot working.
本発明に係るチタン複合材は、引張強度、ヤング率などの機械的特性に優れ、また、溶解工程、および鍛造工程などを経ずに製造可能であるため、製造コストを大幅に低減できる。また、本発明に係るチタン複合材は、鋳塊の表層や底面に多い欠陥部の切削除去や、鍛造後の表面割れや形状の悪い先後端部（クロップ）の除去など、多量のチタン素材を切削除去や切断除去を行うことなく製造できるため、製造歩留りが大幅に向上し、この点からも製造コストが大幅に低減されている。
The titanium composite material according to the present invention is excellent in mechanical properties such as tensile strength and Young's modulus, and can be manufactured without undergoing a melting step, a forging step, and the like, so that the manufacturing cost can be greatly reduced. In addition, the titanium composite material according to the present invention includes a large amount of titanium material such as cutting and removal of many defective portions on the surface layer and bottom surface of the ingot, and removal of surface cracks and badly shaped front and rear ends (crop) after forging. Since it can manufacture without performing cutting removal and cutting removal, a manufacturing yield improves significantly and the manufacturing cost is also reduced significantly also from this point.
本発明に係るチタン複合材およびチタン梱包体を、添付図面を参照しながら説明する。なお、以降の説明では、化学組成に関する「％」は特に断りがない限り「質量％」を意味する。
The titanium composite material and titanium package according to the present invention will be described with reference to the accompanying drawings. In the following description, “%” regarding chemical composition means “% by mass” unless otherwise specified.
１．本発明に係るチタン複合材１の構成
図１は、本発明に係るチタン複合材１の構成の一例を示す説明図である。 1. Configuration ofTitanium Composite 1 According to the Present Invention FIG. 1 is an explanatory diagram showing an example of the configuration of the titanium composite 1 according to the present invention.
図１は、本発明に係るチタン複合材１の構成の一例を示す説明図である。 1. Configuration of
図１に示すように、チタン複合材１は、表層部２，３と内層部４とを備える。以下、各層について説明する。
As shown in FIG. 1, the titanium composite material 1 includes surface layer portions 2 and 3 and an inner layer portion 4. Hereinafter, each layer will be described.
（ａ）表層部２，３
（ａ－１）表層部２，３の化学組成
表層部２，３をなす工業用純チタン材としては、ＪＩＳ１～４種のいずれかに属する化学組成の工業用純チタン材を用いることができる。例えば、表層部２，３は、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部Ｔｉおよび不純物の化学組成を有する。 (A) Surface layer parts 2, 3
(A-1) Chemical composition of the surface layer portions 2 and 3 As the industrial pure titanium material forming the surface layer portions 2 and 3, an industrial pure titanium material having a chemical composition belonging to any of JIS 1-4 can be used. . For example, the surface layer portions 2 and 3 are: C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance It has a chemical composition of Ti and impurities.
（ａ－１）表層部２，３の化学組成
表層部２，３をなす工業用純チタン材としては、ＪＩＳ１～４種のいずれかに属する化学組成の工業用純チタン材を用いることができる。例えば、表層部２，３は、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部Ｔｉおよび不純物の化学組成を有する。 (A)
(A-1) Chemical composition of the
なお、上記のＪＩＳ１種～４種は、ＪＩＳＨ４６００：２０１２に規定されたものとする。ＪＩＳ１種とはＣ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．１５％以下、Ｎ：０．０３％以下、Ｆｅ：０．２０％以下、残部Ｔｉおよび不純物の組成を有する。ＪＩＳ２種とは、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．２０％以下、Ｎ：０．０３％以下、Ｆｅ：０．２５％以下、残部Ｔｉおよび不純物の組成を有する。ＪＩＳ３種とは、Ｃ：０．０８％以下、Ｈ：０．０１４％以下、Ｏ：０．３０％以下、Ｎ：０．０５％以下、Ｆｅ：０．３０％以下、残部Ｔｉおよび不純物の組成を有する。ＪＩＳ４種とは、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４０％以下、Ｎ：０．０５％以下、Ｆｅ：０．５０％以下、残部Ｔｉおよび不純物の組成を有する。
The above JIS types 1 to 4 are defined in JIS 4600: 2012. JIS class 1 is C: 0.08% or less, H: 0.013% or less, O: 0.15% or less, N: 0.03% or less, Fe: 0.20% or less, the balance of Ti and impurities Have JIS type 2 is C: 0.08% or less, H: 0.013% or less, O: 0.20% or less, N: 0.03% or less, Fe: 0.25% or less, the balance of Ti and impurities Having a composition. JIS class 3 means C: 0.08% or less, H: 0.014% or less, O: 0.30% or less, N: 0.05% or less, Fe: 0.30% or less, the balance of Ti and impurities Having a composition. JIS class 4 means C: 0.08% or less, H: 0.013% or less, O: 0.40% or less, N: 0.05% or less, Fe: 0.50% or less, the balance of Ti and impurities Having a composition.
一方、表層部２，３をなすチタン合金材としては、α型チタン合金、α＋β型チタン合金、またはβ型チタン合金を用いることができる。
On the other hand, as the titanium alloy material forming the surface layer portions 2 and 3, an α-type titanium alloy, an α + β-type titanium alloy, or a β-type titanium alloy can be used.
α型チタン合金としては、例えば、Ｔｉ－０．０６％Ｐｄ、Ｔｉ－０．２Ｐｄ、Ｔｉ－０．０２Ｐｄ－０．０５Ｍｍ（ここで、Ｍｍは、ミッシュメタルを指す）、Ｔｉ－０．５Ｎｉ－０．０５Ｒｕ、Ｔｉ－０．５Ｃｕ、Ｔｉ－１．０Ｃｕ、Ｔｉ－１．０Ｃｕ－０．５Ｎｂ、Ｔｉ－１．０Ｃｕ－１．０Ｓｎ－０．３Ｓｉ－０．２５Ｎｂ、Ｔｉ－０．５Ａｌ－０．４５Ｓｉ、Ｔｉ－０．９Ａｌ－０．３５Ｓｉ、Ｔｉ－３Ａｌ－２．５Ｖ、Ｔｉ－５Ａｌ－２．５Ｓｎ、Ｔｉ－６Ａｌ－２Ｓｎ－４Ｚｒ－２Ｍｏ、Ｔｉ－６Ａｌ－２．７５Ｓｎ－４Ｚｒ－０．４Ｍｏ－０．４５Ｓｉなどがある。
Examples of the α-type titanium alloy include Ti-0.06% Pd, Ti-0.2Pd, Ti-0.02Pd-0.05Mm (where Mm represents Misch metal), Ti-0.5Ni. -0.05Ru, Ti-0.5Cu, Ti-1.0Cu, Ti-1.0Cu-0.5Nb, Ti-1.0Cu-1.0Sn-0.3Si-0.25Nb, Ti-0.5Al -0.45Si, Ti-0.9Al-0.35Si, Ti-3Al-2.5V, Ti-5Al-2.5Sn, Ti-6Al-2Sn-4Zr-2Mo, Ti-6Al-2.75Sn-4Zr -0.4Mo-0.45Si.
α＋β型チタン合金としては、例えば、Ｔｉ－６Ａｌ－４Ｖ、Ｔｉ－６Ａｌ－６Ｖ－２Ｓｎ、Ｔｉ－６Ａｌ－７Ｖ、Ｔｉ－３Ａｌ－５Ｖ、Ｔｉ－５Ａｌ－２Ｓｎ－２Ｚｒ－４Ｍｏ－４Ｃｒ、Ｔｉ－６Ａｌ－２Ｓｎ－４Ｚｒ－６Ｍｏ、Ｔｉ－１Ｆｅ－０．３５Ｏ、Ｔｉ－１．５Ｆｅ－０．５Ｏ、Ｔｉ－５Ａｌ－１Ｆｅ、Ｔｉ－５Ａｌ－１Ｆｅ－０．３Ｓｉ、Ｔｉ－５Ａｌ－２Ｆｅ、Ｔｉ－５Ａｌ－２Ｆｅ－０．３Ｓｉ、Ｔｉ－５Ａｌ－２Ｆｅ－３Ｍｏ、Ｔｉ－４．５Ａｌ－２Ｆｅ－２Ｖ－３Ｍｏなどがある。
Examples of α + β type titanium alloys include Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-7V, Ti-3Al-5V, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-6Al. -2Sn-4Zr-6Mo, Ti-1Fe-0.35O, Ti-1.5Fe-0.5O, Ti-5Al-1Fe, Ti-5Al-1Fe-0.3Si, Ti-5Al-2Fe, Ti-5Al -2Fe-0.3Si, Ti-5Al-2Fe-3Mo, Ti-4.5Al-2Fe-2V-3Mo, and the like.
さらに、β型チタン合金としては、例えば、Ｔｉ－１１．５Ｍｏ－６Ｚｒ－４．５Ｓｎ、Ｔｉ－８Ｖ－３Ａｌ－６Ｃｒ－４Ｍｏ－４Ｚｒ、Ｔｉ－１０Ｖ－２Ｆｅ－３Ｍｏ、Ｔｉ－１３Ｖ－１１Ｃｒ－３Ａｌ、Ｔｉ－１５Ｖ－３Ａｌ－３Ｃｒ－３Ｓｎ、Ｔｉ－６．８Ｍｏ－４．５Ｆｅ－１．５Ａｌ、Ｔｉ－２０Ｖ－４Ａｌ－１Ｓｎ、Ｔｉ－２２Ｖ－４Ａｌなどがある。
Further, as the β-type titanium alloy, for example, Ti-11.5Mo-6Zr-4.5Sn, Ti-8V-3Al-6Cr-4Mo-4Zr, Ti-10V-2Fe-3Mo, Ti-13V-11Cr-3Al Ti-15V-3Al-3Cr-3Sn, Ti-6.8Mo-4.5Fe-1.5Al, Ti-20V-4Al-1Sn, Ti-22V-4Al, and the like.
（ａ－２）表層部２，３の厚さ
チタン複合材１は、表層部２，３の厚さが厚過ぎると、内層部４の厚さが薄くなるため、機械的特性向上効果を十分に得られない。このため、表層部２，３の厚さは、好ましくは、チタン複合材１の全厚さに対して片面当たり４０％以下であり、さらに好ましくは、片面当たり２５％以下である。 (A-2) Thickness of the surface layer portions 2 and 3 In the titanium composite material 1, if the thickness of the surface layer portions 2 and 3 is too thick, the thickness of the inner layer portion 4 is reduced, so that the effect of improving the mechanical characteristics is sufficiently obtained. I can't get it. For this reason, the thickness of the surface layer portions 2 and 3 is preferably 40% or less per side with respect to the total thickness of the titanium composite 1, and more preferably 25% or less per side.
チタン複合材１は、表層部２，３の厚さが厚過ぎると、内層部４の厚さが薄くなるため、機械的特性向上効果を十分に得られない。このため、表層部２，３の厚さは、好ましくは、チタン複合材１の全厚さに対して片面当たり４０％以下であり、さらに好ましくは、片面当たり２５％以下である。 (A-2) Thickness of the
一方、表層部２，３が薄い場合は、内層部４の厚さが厚くなるため、機械的特性向上効果は向上する。しかし、表層部２，３が薄過ぎるとチタン複合材１を加工する際に、表層部２，３が割れて内層部４が表面に現れ、内層部４にあるチタン化合物が脱落したり、表面に現れたチタン化合物が起点となって表面割れや端部割れが発生する。また、水等の液体が接すると、内層部４にその液体が侵入するという問題が発生する。このため、表層部２，３の厚さは、０．１ｍｍ以上とするのが好ましい。
On the other hand, when the surface layer portions 2 and 3 are thin, the thickness of the inner layer portion 4 is increased, so that the mechanical property improving effect is improved. However, when the surface layer portions 2 and 3 are too thin, when the titanium composite material 1 is processed, the surface layer portions 2 and 3 are cracked and the inner layer portion 4 appears on the surface, and the titanium compound in the inner layer portion 4 falls off, Surface cracks and edge cracks occur with the titanium compound appearing in Further, when a liquid such as water comes into contact with the liquid, the problem that the liquid enters the inner layer portion 4 occurs. For this reason, it is preferable that the thickness of the surface layer portions 2 and 3 is 0.1 mm or more.
（ｂ）内層部４
内層部４は、チタン４１にチタン化合物４２が分散しており、前記チタン化合物の周囲にそれぞれの構成元素（すなわち、炭化物の周囲に炭素、窒化物の周囲に窒素、または酸化物の周囲に酸素）が拡散した部分（図示省略）を備え、面積率で、０％超３０％以下の空隙４３を有する。 (B)Inner layer part 4
In theinner layer portion 4, a titanium compound 42 is dispersed in titanium 41, and each constituent element (that is, carbon around a carbide, nitrogen around a nitride, or oxygen around an oxide) around the titanium compound. ) Are diffused (not shown), and have a void 43 that is greater than 0% and not more than 30% in terms of area ratio.
内層部４は、チタン４１にチタン化合物４２が分散しており、前記チタン化合物の周囲にそれぞれの構成元素（すなわち、炭化物の周囲に炭素、窒化物の周囲に窒素、または酸化物の周囲に酸素）が拡散した部分（図示省略）を備え、面積率で、０％超３０％以下の空隙４３を有する。 (B)
In the
（ｂ－１）内層部４の化学組成
チタン複合材１の内層部４を構成するチタンとしては、例えば、ＪＩＳ１種～ＪＩＳ４種の工業用純チタンを用いることができる。すなわち、一般的な不純物として、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部がＴｉである工業用純チタンである。 (B-1) Chemical composition of theinner layer part 4 As the titanium constituting the inner layer part 4 of the titanium composite material 1, for example, JIS class 1 to JIS class 4 industrial pure titanium can be used. That is, as general impurities, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, and the balance It is an industrial pure titanium which is Ti.
チタン複合材１の内層部４を構成するチタンとしては、例えば、ＪＩＳ１種～ＪＩＳ４種の工業用純チタンを用いることができる。すなわち、一般的な不純物として、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部がＴｉである工業用純チタンである。 (B-1) Chemical composition of the
特に、ＪＩＳ１～３種の工業用純チタンを使用すれば、十分な加工性を有しており、割れなどが発生せず、熱間加工後に上述の表層部２，３をなす工業用純チタンと一体化したチタン複合材１を得られる。
In particular, the use of JIS 1 to 3 types of industrial pure titanium has sufficient workability, does not generate cracks, etc., and industrial pure titanium that forms the above-mentioned surface portions 2 and 3 after hot working. And the titanium composite material 1 integrated.
上記以外の残部は不純物である。不純物としては、加工性および機械的特性向上効果を減殺しない範囲で含有することができる。上記以外の不純物は、主にスクラップから混入する不純物元素として、Ａｌ，Ｖ，Ｃｒ，Ｎｂ，Ｓｉ，Ｓｎ，ＭｏおよびＣｕ等があり、一般的な不純物元素（Ｃ，Ｎ，Ｆｅ，Ｏ，Ｈ）と併せて、総量で５％以下許容される。
The remainder other than the above is impurities. As an impurity, it can contain in the range which does not reduce processability and a mechanical characteristic improvement effect. Impurities other than the above include Al, V, Cr, Nb, Si, Sn, Mo, Cu, and the like as impurity elements mainly mixed from scrap, and general impurity elements (C, N, Fe, O, H, etc.) In addition, a total amount of 5% or less is allowed.
内層部４は、チタン複合材１に良好な機械的特性を具備させるため、チタンに炭化物、窒化物および酸化物から選択される１種以上のチタン化合物が分散しているものを用いる。内層部４においては、上記の効果を得るために、炭素、窒素および酸素の平均含有量の合計が０．０５～２．０質量％であることが好ましい。それぞれの元素の平均含有量の好ましい範囲と限定理由を述べる。
The inner layer portion 4 is made of a material in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium in order to make the titanium composite 1 have good mechanical properties. In the inner layer part 4, in order to obtain the above effect, the total of the average contents of carbon, nitrogen and oxygen is preferably 0.05 to 2.0% by mass. The preferable range of the average content of each element and the reason for limitation will be described.
［Ｃ：０．００１～０．１％］
Ｃは、その平均濃度が０．００１％未満であると、表層部２，３よりも内層部４の強度を高める効果が殆ど認められず、チタン複合材１の機械的特性を向上できない。一方、Ｃの平均濃度が０．１％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＣの平均濃度は、０．００１～０．１％とするのが好ましい。 [C: 0.001 to 0.1%]
If the average concentration of C is less than 0.001%, the effect of increasing the strength of theinner layer portion 4 over the surface layer portions 2 and 3 is hardly recognized, and the mechanical properties of the titanium composite material 1 cannot be improved. On the other hand, if the average concentration of C exceeds 0.1%, the toughness of the inner layer part 4 is deteriorated, cracks frequently occur during hot working or cold working, and the thickness direction of the inner layer part 4 is divided and peeled off. Thus, the shape of the titanium composite material 1 may not be maintained. Therefore, the average concentration of C in the inner layer portion 4 is preferably 0.001 to 0.1%.
Ｃは、その平均濃度が０．００１％未満であると、表層部２，３よりも内層部４の強度を高める効果が殆ど認められず、チタン複合材１の機械的特性を向上できない。一方、Ｃの平均濃度が０．１％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＣの平均濃度は、０．００１～０．１％とするのが好ましい。 [C: 0.001 to 0.1%]
If the average concentration of C is less than 0.001%, the effect of increasing the strength of the
［Ｎ：０．００１～０．５％］
Ｎは、その平均濃度が０．００１％未満であると、表層部２，３よりも内層部４の強度を高める効果が殆ど認められず、チタン複合材１の特性を向上できない。一方、Ｎの平均濃度が０．５％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＮの平均濃度は、０．００１～０．５％とするのが好ましい。 [N: 0.001 to 0.5%]
When the average concentration of N is less than 0.001%, the effect of increasing the strength of theinner layer portion 4 over the surface layer portions 2 and 3 is hardly recognized, and the characteristics of the titanium composite material 1 cannot be improved. On the other hand, if the average concentration of N exceeds 0.5%, the toughness of the inner layer portion 4 is deteriorated, cracks frequently occur during hot working or cold working, and the thickness direction of the inner layer portion 4 is divided and peeled off. Thus, the shape of the titanium composite material 1 may not be maintained. Therefore, the average concentration of N in the inner layer portion 4 is preferably 0.001 to 0.5%.
Ｎは、その平均濃度が０．００１％未満であると、表層部２，３よりも内層部４の強度を高める効果が殆ど認められず、チタン複合材１の特性を向上できない。一方、Ｎの平均濃度が０．５％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＮの平均濃度は、０．００１～０．５％とするのが好ましい。 [N: 0.001 to 0.5%]
When the average concentration of N is less than 0.001%, the effect of increasing the strength of the
［Ｏ：０．０１～１．０％］
Ｏは、その平均濃度が０．０１％未満であると、表層部２，３よりも内層部４の強度を高める効果を殆ど認められず、チタン複合材１の特性を向上できない。一方、Ｏの平均濃度が１．０％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＯの平均濃度は、０．０１～１．０％とするのが好ましい。 [O: 0.01 to 1.0%]
If the average concentration of O is less than 0.01%, the effect of increasing the strength of theinner layer portion 4 over the surface layer portions 2 and 3 is hardly recognized, and the characteristics of the titanium composite material 1 cannot be improved. On the other hand, when the average concentration of O exceeds 1.0%, the toughness of the inner layer portion 4 is deteriorated, cracks frequently occur during hot working or cold working, and the thickness direction of the inner layer portion 4 is divided and peeled off. Thus, the shape of the titanium composite material 1 may not be maintained. Therefore, the average concentration of O in the inner layer portion 4 is preferably 0.01 to 1.0%.
Ｏは、その平均濃度が０．０１％未満であると、表層部２，３よりも内層部４の強度を高める効果を殆ど認められず、チタン複合材１の特性を向上できない。一方、Ｏの平均濃度が１．０％を超えると、内層部４の靭性を劣化させ、熱間加工や冷間加工時に割れが多発して、内層部４の板厚方向が分断、剥離して、チタン複合材１としての形状を維持できない可能性がある。このため、内層部４のＯの平均濃度は、０．０１～１．０％とするのが好ましい。 [O: 0.01 to 1.0%]
If the average concentration of O is less than 0.01%, the effect of increasing the strength of the
表層部および内層部の成分分析は、公知の方法（例えば、ＪＩＳ Ｈ １６１２（１９９３）、ＪＩＳ Ｈ １６１４（１９９５）、ＪＩＳ Ｈ １６１５（１９９７）、ＪＩＳ Ｈ １６１７（１９９５）、ＪＩＳ Ｈ １６１９（２０１２）、ＪＩＳ Ｈ １６２０（１９９５））により求める。なお、この際、チタン複合材から表層部および内層部をそれぞれ切り出してから測定を行う。表層部は切削等で加工して得た切粉等から、内層部は表層削除後の残材から分析試料を採取して分析するのが効率的である。分析試料は、表層部、内層部の板厚方向の中心部から０．５ｇ以上を採取する。表層部または内層部の厚さが薄く十分な量の切粉を得られない場合には、チタン複合材の全体の成分分析を行いその分析値と、表層部または内層部のいずれかの分析値と、それぞれの板厚から、表層または内層部の成分を算出（逆算）してもよい。
Component analysis of the surface layer portion and the inner layer portion 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)). At this time, measurement is performed after cutting out the surface layer portion and the inner layer portion from the titanium composite material. It is efficient to collect and analyze an analysis sample from a chip obtained by machining the surface layer portion and the inner layer portion from the remaining material after the surface layer is deleted. As an analysis sample, 0.5 g or more is collected from the center portion in the thickness direction of the surface layer portion and the inner layer portion. If the surface layer or inner layer is thin and a sufficient amount of chips cannot be obtained, analyze the entire composition of the titanium composite and its analysis value and either the surface layer or inner layer analysis value And the component of the surface layer or the inner layer part may be calculated (reverse calculation) from each plate thickness.
（ｂ－２）内層部４の空隙率
チタン複合材１の空隙４３の空隙率が多過ぎると、バルク金属としての機械的特性（強度や延性）が得られない。一方、空隙４３は少ないほど望ましいが、空隙を完全に圧着させるためには、大圧下が必要となる。その結果、製造されるチタン複合材１の形状（厚さ）が制限され、さらには、製造コストが嵩む。 (B-2) Porosity of theinner layer portion 4 If the porosity of the void 43 of the titanium composite material 1 is too large, mechanical properties (strength and ductility) as a bulk metal cannot be obtained. On the other hand, the smaller the gap 43, the better. However, in order to completely press the gap, a large pressure is required. As a result, the shape (thickness) of the titanium composite material 1 to be manufactured is limited, and the manufacturing cost increases.
チタン複合材１の空隙４３の空隙率が多過ぎると、バルク金属としての機械的特性（強度や延性）が得られない。一方、空隙４３は少ないほど望ましいが、空隙を完全に圧着させるためには、大圧下が必要となる。その結果、製造されるチタン複合材１の形状（厚さ）が制限され、さらには、製造コストが嵩む。 (B-2) Porosity of the
一方、チタン複合材１としての構造を維持するのに十分な機械的特性（強度や延性など）を有する程度に空隙４３が含有される場合には、内層部４の密度が低くなり、チタン複合材１の軽量化を図ることができる。
On the other hand, when the voids 43 are contained to such an extent that the mechanical properties (strength, ductility, etc.) sufficient to maintain the structure as the titanium composite material 1 are contained, the density of the inner layer portion 4 becomes low, and the titanium composite The weight of the material 1 can be reduced.
以上のように、バルク金属としての機械的特性が重要な場合には空隙率を低くし、一方、チタン複合材１の軽量化を優先する場合には、空隙率を高くする。このように、用途に応じて、空隙率を選択することが可能である。この際の空隙率の範囲は、０％超３０％以下であることが好ましく、０％超１０％以下がより好ましい。なお、空隙率を１０％以下とすることにより、一般的な工業用純チタンと遜色のない機械的特性を具備することができる。
As described above, when the mechanical properties as a bulk metal are important, the porosity is lowered. On the other hand, when the weight reduction of the titanium composite 1 is prioritized, the porosity is increased. Thus, the porosity can be selected according to the application. In this case, the range of the porosity is preferably more than 0% and 30% or less, more preferably more than 0% and 10% or less. In addition, by setting the porosity to 10% or less, it is possible to have mechanical characteristics comparable to general industrial pure titanium.
チタン複合材１の内層部４に残存する空隙４３の割合（空隙率）は、次のように算出される。チタン複合材１の長さ方向（圧延方向）に平行な厚さ断面が観察できるように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観察面を研磨し（鏡面化仕上げ）、観察用試料に仕上げる。
The ratio (void ratio) of the voids 43 remaining in the inner layer portion 4 of the titanium composite material 1 is calculated as follows. After embedding in the resin so that a cross section with a thickness parallel to the length direction (rolling direction) of the titanium composite material 1 can be observed, the observation surface is polished with a diamond or alumina suspension (mirror finish) and observed. Finish the sample.
この鏡面化仕上げを行った観察用試料は、光学顕微鏡で異なる位置の２０か所の厚さ中心部について、撮影される。ここで、中心部とは、チタン複合材１が板の場合は、板厚中心であり、丸棒の場合は円断面の中心である。その光学顕微鏡写真にて観察される空隙４３の面積割合を測定して、２０枚の写真の空隙率の値を平均した結果を空隙率として算出する。
The observation sample that has been subjected to the mirror finish is photographed at 20 thickness centers at different positions with an optical microscope. Here, the center portion is the thickness center when the titanium composite material 1 is a plate, and the center of the circular cross section when the titanium composite material 1 is a round bar. The area ratio of the voids 43 observed in the optical micrograph is measured, and the result of averaging the porosity values of the 20 photographs is calculated as the void ratio.
なお、光学顕微鏡で組織写真を撮影する際には、チタン複合材１の空隙の大きさ、または空隙率に応じて適正な倍率を選択する。例えば、空隙率が１％以下の場合は、空隙が小さいので、５００倍程度の高倍率で観察して、写真撮影を行うのが好ましい。空隙率が１０％以上の場合は、大きな空隙が多くなるので、２０倍程度の低倍率で観察を行い、写真撮影を行うのが好ましい。また、空隙が小さくなるような空隙率が１％以下の場合、偏光観察が可能な微分干渉顕微鏡を用いることにより、通常の光学顕微鏡よりもより明瞭に観察することができる。
In addition, when taking a structure | tissue photograph with an optical microscope, a suitable magnification is selected according to the magnitude | size of the space | gap of the titanium composite 1, or the porosity. For example, when the porosity is 1% or less, since the void is small, it is preferable to take a picture while observing at a high magnification of about 500 times. When the porosity is 10% or more, there are many large voids, so it is preferable to perform photography at a low magnification of about 20 times. Further, when the void ratio is 1% or less so that the voids become small, it is possible to observe more clearly than a normal optical microscope by using a differential interference microscope capable of observing polarized light.
（ｂ－３）内層部４の組織
図１に示すように、チタン複合材１中の内層部４には、チタン化合物４２が多く含まれている。このチタン化合物４２は、チタン複合材１の製造過程における熱間加工などにより、チタン化合物４２の周囲にそれぞれの構成元素（すなわち、炭化物の周囲に炭素、窒化物の周囲に窒素、または酸化物の周囲に酸素）がチタン４１に拡散するが、チタン４１に固溶できないそれぞれの構成元素は、チタン化合物４２としてチタン材４１に分散した状態で残存する。このとき、チタン化合物４２は、加工（圧延）方向に並び、筋状化合物集合体４２ａを構成している。また、チタン化合物４２は、完全に化合物を形成しているもののほか、内部に炭素が存在している化合物を含む。例えば、チタン化合物の素材として炭素を用いた場合、熱間圧延等の製造過程において炭素がチタンと反応してチタン化合物を形成するが、そのチタン化合物の内部にチタンと反応しきれなかった炭素が残存することがある。 (B-3) Structure ofInner Layer Part 4 As shown in FIG. 1, the inner layer part 4 in the titanium composite 1 contains a large amount of the titanium compound 42. The titanium compound 42 is made of each constituent element (that is, carbon around the carbide, nitrogen around the nitride, nitrogen, or oxide) around the titanium compound 42 by hot working or the like in the manufacturing process of the titanium composite 1. Each constituent element that cannot be dissolved in the titanium 41 remains as a titanium compound 42 in a dispersed state in the titanium material 41. At this time, the titanium compound 42 is aligned in the processing (rolling) direction and constitutes a streak-like compound aggregate 42a. Moreover, the titanium compound 42 includes a compound in which carbon is present in addition to a compound that completely forms a compound. For example, when carbon is used as a material for a titanium compound, carbon reacts with titanium in a manufacturing process such as hot rolling to form a titanium compound, but the carbon that has not reacted with titanium inside the titanium compound. May remain.
図１に示すように、チタン複合材１中の内層部４には、チタン化合物４２が多く含まれている。このチタン化合物４２は、チタン複合材１の製造過程における熱間加工などにより、チタン化合物４２の周囲にそれぞれの構成元素（すなわち、炭化物の周囲に炭素、窒化物の周囲に窒素、または酸化物の周囲に酸素）がチタン４１に拡散するが、チタン４１に固溶できないそれぞれの構成元素は、チタン化合物４２としてチタン材４１に分散した状態で残存する。このとき、チタン化合物４２は、加工（圧延）方向に並び、筋状化合物集合体４２ａを構成している。また、チタン化合物４２は、完全に化合物を形成しているもののほか、内部に炭素が存在している化合物を含む。例えば、チタン化合物の素材として炭素を用いた場合、熱間圧延等の製造過程において炭素がチタンと反応してチタン化合物を形成するが、そのチタン化合物の内部にチタンと反応しきれなかった炭素が残存することがある。 (B-3) Structure of
（ｂ－３－１）チタン化合物の形状
図２は、筋状化合物集合体４２ａを模式的に示す図である。図２に示すように、筋状化合物集合体４２ａは、チタン化合物４２の粒の中心間距離を圧延方向に投影した距離Ｄ（以下、「粒子間距離」という。）が２０μｍ以下である複数のチタン化合物４２の集合体を意味する。なお、本明細書において、粒子間距離が２０μｍを超える場合には別の筋状化合物集合体として扱う。 (B-3-1) Shape of Titanium Compound FIG. 2 is a diagram schematically showing thestreak compound aggregate 42a. As shown in FIG. 2, the streak-like compound aggregate 42a has a plurality of distances D (hereinafter referred to as “inter-particle distances”) obtained by projecting the distance between the centers of the grains of the titanium compound 42 in the rolling direction to 20 μm or less. An aggregate of titanium compounds 42 is meant. In the present specification, when the interparticle distance exceeds 20 μm, it is treated as another streak compound aggregate.
図２は、筋状化合物集合体４２ａを模式的に示す図である。図２に示すように、筋状化合物集合体４２ａは、チタン化合物４２の粒の中心間距離を圧延方向に投影した距離Ｄ（以下、「粒子間距離」という。）が２０μｍ以下である複数のチタン化合物４２の集合体を意味する。なお、本明細書において、粒子間距離が２０μｍを超える場合には別の筋状化合物集合体として扱う。 (B-3-1) Shape of Titanium Compound FIG. 2 is a diagram schematically showing the
筋状化合物集合体４２ａは、その厚さｔ（すなわち、圧縮加工方向の大きさ。）が１００μｍ以下であることが好ましい。この厚さが１００μｍを超えると、チタン複合材を加工する際に、チタン化合物４２を起点に割れが発生する可能性が大きくなるからである。一方、筋状化合物集合体４２ａは、その長さＬ（すなわち、加工方向の大きさ）は、厚さ方向の大きさ（厚さ）ｔの２．０倍以上（すなわち、Ｌ／ｔ≧２．０）であることが好ましく、３．０倍以上（すなわち、Ｌ／ｔ≧３．０）であることがより好ましい。長さＬが小さいと、引張応力を受けた際に、このチタン化合物を起点に内層部が破断しやすくなるからである。なお、Ｌ／ｔ≦１００とするのが好ましく、Ｌ／ｔ≦４０とするのがより好ましい。
It is preferable that the thickness t (that is, the size in the compression processing direction) of the streak compound aggregate 42a is 100 μm or less. This is because when the thickness exceeds 100 μm, the possibility of cracking starting from the titanium compound 42 increases when the titanium composite material is processed. On the other hand, the length L (that is, the size in the processing direction) of the streak compound aggregate 42a is 2.0 times or more the thickness (the thickness) t in the thickness direction (that is, L / t ≧ 2). 0.0), more preferably 3.0 times or more (that is, L / t ≧ 3.0). This is because when the length L is small, the inner layer portion is likely to be broken starting from this titanium compound when subjected to tensile stress. Note that L / t ≦ 100 is preferable, and L / t ≦ 40 is more preferable.
筋状化合物集合体４２ａの大きさ（長さＬおよび厚さｔ）は、次のように算出される。チタン複合材１の長さ方向（圧延方向）および厚さ方向に平行な断面（厚さ断面）を観察面とするように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観察面を研磨して観察用試料に仕上げる。
The size (length L and thickness t) of the streak-like compound aggregate 42a is calculated as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation.
光学顕微鏡を用いて、上記観察面の厚さ中心部の異なる位置の２０か所を写真撮影する。ここで、厚さ中心部は、チタン複合材１が板である場合は板厚中心部であり、丸棒である場合は円断面の中心である。得られた２０枚の写真において、筋状化合物集合体４２ａの長さＬと厚さｔを測定し、それぞれの値の平均値を長さＬと厚さｔとし、Ｌ／ｔを計算する。
Using an optical microscope, take pictures of 20 locations at different positions in the center of the thickness of the observation surface. Here, the thickness center portion is the plate thickness center portion when the titanium composite material 1 is a plate, and is the center of the circular cross section when the titanium composite material 1 is a round bar. In the obtained 20 photographs, the length L and the thickness t of the streak-like compound aggregate 42a are measured, and the average value of each value is taken as the length L and the thickness t, and L / t is calculated.
（ｂ－３－２）拡散層の存在
チタン化合物４２のそれぞれの粒の周囲には、それぞれの構成元素（すなわち、炭化物の場合は炭素、窒化物の場合は窒素、酸化物の場合は酸素）の拡散層が存在する。拡散層とは、内層部４のチタン４１に分散したチタン化合物４２において、その構成元素（炭素、窒素または酸素）がチタン化合物４２を中心として周辺のチタン４１に拡散し、濃度勾配が形成された層をいう。 (B-3-2) Presence of diffusion layer Around each grain of thetitanium compound 42, each constituent element (that is, carbon for carbide, nitrogen for nitride, oxygen for oxide) There is a diffusion layer. The diffusion layer is a titanium compound 42 dispersed in titanium 41 in the inner layer portion 4, and its constituent elements (carbon, nitrogen or oxygen) diffuse into the surrounding titanium 41 with the titanium compound 42 as the center, and a concentration gradient is formed. Refers to the layer.
チタン化合物４２のそれぞれの粒の周囲には、それぞれの構成元素（すなわち、炭化物の場合は炭素、窒化物の場合は窒素、酸化物の場合は酸素）の拡散層が存在する。拡散層とは、内層部４のチタン４１に分散したチタン化合物４２において、その構成元素（炭素、窒素または酸素）がチタン化合物４２を中心として周辺のチタン４１に拡散し、濃度勾配が形成された層をいう。 (B-3-2) Presence of diffusion layer Around each grain of the
図３は、チタン複合材１の長さ方向（圧延方向）および厚さ方向に平行な断面（厚さ断面）において、１つの粒の厚さ方向の距離とその周囲の構成元素濃度分布の概念を示した図である。拡散層は、チタン複合材１を製造する過程で、加熱保持された際（熱間圧延前の加熱、熱間圧延中、熱間圧延後の熱処理等）に、チタン化合物４２の粒から周囲のチタン４１に各構成元素が拡散してできた層である。図３に示すように、拡散層は、内層部４のチタン４１に含まれている各構成元素の値よりも多く含まれている。この拡散層が存在することにより、内層部４のチタン化合物４２の粒とチタン４１が強固に結合する。このため、チタン複合材１を加工する際にチタン化合物４２を起点に割れることがない。
FIG. 3 shows a concept of the distance in the thickness direction of one grain and the concentration distribution of constituent elements around it in a cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite material 1. FIG. When the diffusion layer is heated and held in the process of manufacturing the titanium composite material 1 (heating before hot rolling, during hot rolling, heat treatment after hot rolling, etc.), This is a layer formed by diffusing each constituent element in titanium 41. As shown in FIG. 3, the diffusion layer is contained in a larger amount than the value of each constituent element contained in the titanium 41 of the inner layer part 4. Due to the presence of this diffusion layer, the grains of the titanium compound 42 in the inner layer portion 4 and the titanium 41 are firmly bonded. For this reason, when the titanium composite material 1 is processed, the titanium compound 42 does not break from the starting point.
この拡散層は次のようにして把握できる。チタン複合材１の長さ方向（圧延方向）および厚さ方向に平行な断面（厚さ断面）を観察面とするように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観察面を研磨して観察用試料に仕上げる。ＥＰＭＡを用いて、上記観察用試料で観察されるチタン化合物４２の粒が中心になるようにして厚さ方向に線分析を行う。分析の対象は、それぞれの構成元素（すなわち、炭化物の場合は炭素、窒化物の場合は窒素、酸化物の場合は酸素）である。内層部４のチタン４１の値を基準にしてそれよりも濃度の高く、粒子を除いた領域が拡散層である。
This diffusion layer can be grasped as follows. After embedding in the resin so that the cross section (thickness cross section) parallel to the length direction (rolling direction) and the thickness direction of the titanium composite 1 is the observation surface, the observation surface is formed using diamond or alumina suspension. Polish to finish the sample for observation. Using EPMA, line analysis is performed in the thickness direction so that the grain of the titanium compound 42 observed in the observation sample is centered. The object of analysis is each constituent element (that is, carbon in the case of carbide, nitrogen in the case of nitride, oxygen in the case of oxide). A region having a higher concentration than the value of titanium 41 in the inner layer portion 4 and excluding particles is a diffusion layer.
前記の拡散層の厚さは、色々な因子によって変化する。例えば、チタン化合物を添加する場合、(１) チタン化合物の分解、(２)周辺へのそれぞれの構成元素の拡散、によって形成されるために、チタン化合物の分解速度とそれぞれの構成元素のチタン材内での拡散速度によって変化する。また、製造時の熱履歴によっても変化する。さらに、熱間圧延素材としての梱包体の加熱時における、スポンジチタン等とチタン化合物の接触程度によっても変化する。よって、拡散層の厚さは同一材の中でも色々な拡散層の厚さを有することになり、一義的に決定することは困難であるが、チタン化合物やそれぞれの構成元素が存在する、または存在した部分を中心に、少なからず形成される。
The thickness of the diffusion layer varies depending on various factors. For example, when a titanium compound is added, since it is formed by (1) decomposition of the titanium compound and (2) diffusion of each constituent element to the periphery, the decomposition rate of the titanium compound and the titanium material of each constituent element Varies depending on the diffusion rate. It also varies depending on the thermal history during manufacture. Furthermore, it changes also with the contact degree of sponge titanium etc. and a titanium compound at the time of the heating of the package as a hot rolling raw material. Therefore, the thickness of the diffusion layer has various diffusion layer thicknesses within the same material, and it is difficult to uniquely determine, but the titanium compound and each constituent element exist or exist. It is formed not a little around the part.
（ｂ－４）内層部４の厚さ
チタン複合材１の全厚さに対する内層部４の厚さが厚いほど、機械的特性は向上するので、チタン複合材１の全厚さに対して２０％超とするのが好ましく、より好ましくは５０％超である。一方、厚すぎると、加工性が劣化するので、内層部４の厚さは、チタン複合材１の全厚さに対して９５％以下とするのが好ましい。 (B-4) Thickness of theinner layer portion 4 As the thickness of the inner layer portion 4 with respect to the total thickness of the titanium composite material 1 increases, the mechanical characteristics improve. % Is preferable, and more preferably 50%. On the other hand, if the thickness is too large, the workability deteriorates. Therefore, the thickness of the inner layer portion 4 is preferably 95% or less with respect to the total thickness of the titanium composite material 1.
チタン複合材１の全厚さに対する内層部４の厚さが厚いほど、機械的特性は向上するので、チタン複合材１の全厚さに対して２０％超とするのが好ましく、より好ましくは５０％超である。一方、厚すぎると、加工性が劣化するので、内層部４の厚さは、チタン複合材１の全厚さに対して９５％以下とするのが好ましい。 (B-4) Thickness of the
２．本発明に係る梱包体５の構成
チタン梱包体５は、チタン梱包材６と充填材７，８とを備える。チタン梱包体５の形状は、特定の形状に限られるものではないが、製造されるチタン複合材１の形状によって決められる。板材のチタン複合材１を製造する場合は、直方体形状のチタン梱包体５を用いる。また、丸棒や線材、さらには押出材のチタン複合材１を製造する場合には、円柱形または八角柱等多角柱形状のチタン梱包体５を用いる。チタン梱包体５の大きさは、製品の大きさ（厚さ、幅や長さ）および製造量（質量）により決められる。 2. Configuration ofPacking Body 5 According to the Present Invention Titanium packing body 5 includes a titanium packing material 6 and fillers 7 and 8. The shape of the titanium package 5 is not limited to a specific shape, but is determined by the shape of the titanium composite material 1 to be manufactured. When manufacturing the titanium composite material 1 of a plate material, a rectangular parallelepiped titanium package 5 is used. Moreover, when manufacturing the titanium composite material 1 of a round bar, a wire, and also an extruded material, a cylindrical packing or a polygonal column shape titanium packing 5 such as an octagonal column is used. The size of the titanium package 5 is determined by the product size (thickness, width and length) and the production amount (mass).
チタン梱包体５は、チタン梱包材６と充填材７，８とを備える。チタン梱包体５の形状は、特定の形状に限られるものではないが、製造されるチタン複合材１の形状によって決められる。板材のチタン複合材１を製造する場合は、直方体形状のチタン梱包体５を用いる。また、丸棒や線材、さらには押出材のチタン複合材１を製造する場合には、円柱形または八角柱等多角柱形状のチタン梱包体５を用いる。チタン梱包体５の大きさは、製品の大きさ（厚さ、幅や長さ）および製造量（質量）により決められる。 2. Configuration of
（ａ）チタン梱包材６
（ａ－１）チタン梱包材６化学組成
チタン梱包材６は、チタン複合材１の表層部２，３と同様、ＪＩＳ１種～ＪＩＳ４種に属する工業用純チタンまたはチタン合金材を用いる。 (A)Titanium packing material 6
(A-1)Titanium Packing Material 6 Chemical Composition The titanium packing material 6 is made of industrial pure titanium or titanium alloy material belonging to JIS class 1 to JIS class 4, similar to the surface layers 2 and 3 of the titanium composite material 1.
（ａ－１）チタン梱包材６化学組成
チタン梱包材６は、チタン複合材１の表層部２，３と同様、ＪＩＳ１種～ＪＩＳ４種に属する工業用純チタンまたはチタン合金材を用いる。 (A)
(A-1)
（ａ－２）チタン梱包材６形状
チタン梱包材６の形状は、熱間加工用素材として用いられるチタン梱包体５の形状に依存するため、特に定形はなく、板材や管材などを用いることができる。 (A-2)Titanium packing material 6 shape Since the shape of the titanium packing material 6 depends on the shape of the titanium packing body 5 used as a material for hot working, there is no particular shape, and a plate material, a pipe material, or the like can be used. it can.
チタン梱包材６の形状は、熱間加工用素材として用いられるチタン梱包体５の形状に依存するため、特に定形はなく、板材や管材などを用いることができる。 (A-2)
熱間加工および冷間加工、焼鈍などの製造工程を経て製造されるチタン複合材１に優れた表面性状、内層部４の保持、および加工性を具備させるためには、チタン梱包材６の厚さが重要となる。
In order to make the titanium composite 1 manufactured through manufacturing processes such as hot processing, cold processing, and annealing have excellent surface properties, retention of the inner layer portion 4, and workability, the thickness of the titanium packing material 6 Is important.
チタン梱包材６の厚さが１ｍｍ未満と薄い場合には、塑性変形に伴って熱間加工の途中で、チタン梱包材６が破断し、チタン梱包体５内部の一部が脱落する。この場合、同時に真空が破れて、チタン梱包体５の内部に充填されているチタン材７の酸化が生じる。また、チタン梱包体５の内部に充填されたチタン材７の起伏がチタン梱包体５の表面に転写され、熱間加工中に大きな表面起伏を生じるおそれもある。
When the thickness of the titanium packing material 6 is as thin as less than 1 mm, the titanium packing material 6 is broken in the course of hot working along with plastic deformation, and a part of the titanium packing body 5 falls off. In this case, the vacuum is broken at the same time, and the titanium material 7 filled in the titanium package 5 is oxidized. Further, the undulations of the titanium material 7 filled in the titanium package 5 are transferred to the surface of the titanium package 5, and there is a possibility that a large surface undulation may occur during hot working.
これらの結果、製造されるチタン複合材１は、表面性状または延性などの機械的特性が劣化する。さらに、チタン梱包材６が過度に薄くなると、内部に充填したチタン材７の重量を支え切れないおそれがある。このため、室温や熱間保持または加工中にチタン梱包体５の剛性が不足して変形するおそれがある。
As a result, the manufactured titanium composite material 1 deteriorates mechanical properties such as surface properties or ductility. Furthermore, when the titanium packing material 6 becomes too thin, there is a possibility that the weight of the titanium material 7 filled therein cannot be supported. For this reason, there exists a possibility that the rigidity of the titanium package 5 may be insufficient and deform during room temperature, hot holding or processing.
これら問題が発生することなく熱間加工を行うことができ、優れた表面性状、内層部４の保持および加工性を具備したチタン複合材１を製造するために、チタン梱包材６の厚さは、好ましくは１ｍｍ以上であり、より好ましくは２ｍｍ以上である。
In order to manufacture the titanium composite material 1 that can be hot-worked without causing these problems and has excellent surface properties, retention of the inner layer portion 4 and workability, the thickness of the titanium packing material 6 is , Preferably it is 1 mm or more, More preferably, it is 2 mm or more.
さらに、チタン梱包材６の厚さは、チタン梱包体５の全厚さの２５％以下が好ましい。チタン梱包材６の厚さが、チタン梱包体５の全厚さの２５％より厚いと、製造上の問題は特にないものの、チタン梱包体５の全厚さに占めるチタン梱包材６の割合が大きくなり、内部、または内層部４の厚さが薄くなる。このため、チタン梱包体５内部のチタン化合物量が少なくなり、機械的特性向上効果が低くなるため好ましくない。
Furthermore, the thickness of the titanium packing material 6 is preferably 25% or less of the total thickness of the titanium packing body 5. If the thickness of the titanium packing material 6 is greater than 25% of the total thickness of the titanium packing body 5, there is no particular problem in manufacturing, but the ratio of the titanium packing material 6 to the total thickness of the titanium packing body 5 is It becomes large and the thickness of the inside or the inner layer part 4 becomes thin. For this reason, the amount of the titanium compound in the titanium package 5 is reduced, and the effect of improving the mechanical properties is lowered, which is not preferable.
（ｂ）充填材７，８
（ｂ－１）チタン材７
充填材としてのチタン材７は、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上である。 (B) Fillers 7 and 8
(B-1)Titanium material 7
Thetitanium material 7 as the filler is at least one selected from sponge titanium, titanium briquette and titanium scrap.
（ｂ－１）チタン材７
充填材としてのチタン材７は、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上である。 (B)
(B-1)
The
（ｂ－１－１）チタン材７の化学組成
チタン材７の化学組成は、ＪＩＳ１種～ＪＩＳ４種に相当する工業用純チタンを用いることができる。すなわち、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部Ｔｉおよび不純物の化学組成を有する。 (B-1-1) Chemical Composition ofTitanium Material 7 As the chemical composition of the titanium material 7, industrially pure titanium corresponding to JIS class 1 to JIS class 4 can be used. That is, C: 0.08% or less, H: 0.013% or less, O: 0.4% or less, N: 0.05% or less, Fe: 0.5% or less, the balance Ti and the chemical composition of impurities Have.
チタン材７の化学組成は、ＪＩＳ１種～ＪＩＳ４種に相当する工業用純チタンを用いることができる。すなわち、Ｃ：０．０８％以下、Ｈ：０．０１３％以下、Ｏ：０．４％以下、Ｎ：０．０５％以下、Ｆｅ：０．５％以下、残部Ｔｉおよび不純物の化学組成を有する。 (B-1-1) Chemical Composition of
（ｂ－１－２）チタン材７の形状
チタン材７としては、従来のクロール法などの製錬工程により製造された通常のスポンジチタンを用いることができる。その大きさは、平均粒径で２０ｍｍ以下であることが好ましい。平均粒径が２０ｍｍより大きいと、チタン化合物等の粉末８と均一に混合し難く、熱間加工によって製造したチタン複合材１の内層部４内でチタン化合物のむらを生じるおそれがある。一方、平均粒径が小さい場合には、特性面では問題はないが、チタン材７の平均粒径が０．５ｍｍ未満では、破砕するのに時間がかかり、微細な粉塵の発生も多く飛散するため、製造効率が悪くなる。このため、チタン材の平均粒径は０．５ｍｍ以上であることが好ましい。 (B-1-2) Shape ofTitanium Material 7 As the titanium material 7, normal sponge titanium produced by a refining process such as a conventional crawl method can be used. The size is preferably 20 mm or less in terms of average particle size. When the average particle size is larger than 20 mm, it is difficult to uniformly mix with the powder 8 such as a titanium compound, and there is a possibility that unevenness of the titanium compound occurs in the inner layer portion 4 of the titanium composite 1 manufactured by hot working. On the other hand, if the average particle size is small, there is no problem in terms of characteristics, but if the average particle size of the titanium material 7 is less than 0.5 mm, it takes time to crush and a lot of fine dust is scattered. Therefore, the production efficiency is deteriorated. For this reason, it is preferable that the average particle diameter of a titanium material is 0.5 mm or more.
チタン材７としては、従来のクロール法などの製錬工程により製造された通常のスポンジチタンを用いることができる。その大きさは、平均粒径で２０ｍｍ以下であることが好ましい。平均粒径が２０ｍｍより大きいと、チタン化合物等の粉末８と均一に混合し難く、熱間加工によって製造したチタン複合材１の内層部４内でチタン化合物のむらを生じるおそれがある。一方、平均粒径が小さい場合には、特性面では問題はないが、チタン材７の平均粒径が０．５ｍｍ未満では、破砕するのに時間がかかり、微細な粉塵の発生も多く飛散するため、製造効率が悪くなる。このため、チタン材の平均粒径は０．５ｍｍ以上であることが好ましい。 (B-1-2) Shape of
チタン材７としては、チタンスクラップを用いることできる。例えば、チタンスクラップは、工業用純チタン材の製造工程で発生する製品にならない端材、工業用純チタン素材を製品形状とするために切削、研削した際に発生するチタン切粉、製品として使用した後の不要になった工業用純チタン材等である。チタンスクラップは、大き過ぎると、搬送し難い、チタン梱包体５に入れ難いといった問題があるので、適宜切断するのが望ましい。
As the titanium material 7, titanium scrap can be used. For example, titanium scrap is used as a scrap that does not become a product generated in the manufacturing process of industrial pure titanium material, titanium chips generated when cutting and grinding to make industrial pure titanium material into a product shape, product It is a pure titanium material for industrial use that has become unnecessary after the processing. If the titanium scrap is too large, there is a problem that it is difficult to convey and difficult to put in the titanium package 5.
スポンジチタンまたはチタンスクラップは塊状であるため、素材の間には空隙（すきま）９がある。スポンジチタン等のハンドリング性向上、またはこれら空隙を少なくするために、予めスポンジチタン等およびチタン化合物等の粉末８を混合後に圧縮成形して、図５に示すようなブリケット１０としてからチタン梱包体５に入れてもよい。
Since sponge titanium or titanium scrap is in a lump shape, there is a gap (gap) 9 between the materials. In order to improve the handleability of sponge titanium or the like, or to reduce these voids, powder 8 such as sponge titanium and titanium compound is mixed in advance and then compression molded to form briquette 10 as shown in FIG. You may put in.
（ｂ－２）チタン化合物等の粉末８
（ｂ－２－１）チタン化合物等の粉末８の化学組成
チタン化合物等の粉末８は、例えば、炭化物の場合、炭素粉末、ＴｉＣ粉末等が例示され、窒化物の場合、ＴｉＮ粉末のほか、Ｆｅ３Ｎ粉末、Ｆｅ４Ｎ粉末等（ただし、内層部４のチタンのＦｅ濃度がＪＩＳ規格を超えてはならない。）が例示され、酸化物の場合、ＴｉＯ粉末、ＴｉＯ２粉末、Ｔｉ２Ｏ３粉末のほか、ＦｅＯ粉末、Ｆｅ２Ｏ３粉末やＦｅ３Ｏ４粉末等（ただし、内層部４のチタンのＦｅ濃度がＪＩＳ規格を超えてはならない。）が例示される。これらの粉末８は、市販されているものを用いればよい。 (B-2) Powder of titanium compound or the like 8
(B-2-1) Chemical composition ofpowder 8 such as titanium compound Examples of the powder 8 such as titanium compound include carbon powder and TiC powder in the case of carbide, and TiN powder in the case of nitride. Fe 3 N powder, Fe 4 N powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 should not exceed the JIS standard) are exemplified. In the case of an oxide, TiO powder, TiO 2 powder, Ti 2 O In addition to the three powders, FeO powder, Fe 2 O 3 powder, Fe 3 O 4 powder, etc. (however, the Fe concentration of titanium in the inner layer portion 4 must not exceed the JIS standard) are exemplified. What is necessary is just to use what is marketed for these powders 8.
（ｂ－２－１）チタン化合物等の粉末８の化学組成
チタン化合物等の粉末８は、例えば、炭化物の場合、炭素粉末、ＴｉＣ粉末等が例示され、窒化物の場合、ＴｉＮ粉末のほか、Ｆｅ３Ｎ粉末、Ｆｅ４Ｎ粉末等（ただし、内層部４のチタンのＦｅ濃度がＪＩＳ規格を超えてはならない。）が例示され、酸化物の場合、ＴｉＯ粉末、ＴｉＯ２粉末、Ｔｉ２Ｏ３粉末のほか、ＦｅＯ粉末、Ｆｅ２Ｏ３粉末やＦｅ３Ｏ４粉末等（ただし、内層部４のチタンのＦｅ濃度がＪＩＳ規格を超えてはならない。）が例示される。これらの粉末８は、市販されているものを用いればよい。 (B-2) Powder of titanium compound or the like 8
(B-2-1) Chemical composition of
（ｂ－２－２）チタン化合物等の粉末８の形状
チタン化合物等の粉末８の平均粒径が５０μｍを超えると、チタン材７と均一に混合し難い。よって、チタン複合材１の内層部４内でチタン化合物を均一に分散させることができなくなる。このため、チタン化合物等の粉末８の平均粒径は、好ましくは５０μｍ以下である。 (B-2-2) Shape ofPowder 8 such as Titanium Compound When the average particle diameter of the powder 8 such as a titanium compound exceeds 50 μm, it is difficult to uniformly mix with the titanium material 7. Therefore, the titanium compound cannot be uniformly dispersed in the inner layer portion 4 of the titanium composite material 1. For this reason, the average particle diameter of the powder 8 such as a titanium compound is preferably 50 μm or less.
チタン化合物等の粉末８の平均粒径が５０μｍを超えると、チタン材７と均一に混合し難い。よって、チタン複合材１の内層部４内でチタン化合物を均一に分散させることができなくなる。このため、チタン化合物等の粉末８の平均粒径は、好ましくは５０μｍ以下である。 (B-2-2) Shape of
一方、チタン化合物等の粉末８の平均粒径がより小さい場合には特性面では問題はないものの、小さ過ぎると、チタン材７と混合する際、またはチタン梱包体５中に充填する際に、粉塵の飛散が問題になって作業に支障をきたすおそれがある。このため、チタン化合物等の粉末８の平均粒径は０．１μｍ以上であることが好ましい。
On the other hand, if the average particle size of the powder 8 such as a titanium compound is smaller, there is no problem in terms of characteristics, but if it is too small, when mixing with the titanium material 7 or filling in the titanium package 5, There is a risk that the scattering of dust may cause problems. For this reason, it is preferable that the average particle diameter of the powder 8 such as a titanium compound is 0.1 μm or more.
（Ｃ）梱包体５の内部圧力
チタン梱包体５内の空隙４３に空気が残存していると、熱間加工前の加熱時にチタン材７が酸化・窒化してしまい、製造されるチタン複合材１の延性が低下する。このため、チタン梱包体５内を減圧して高真空とすることが有効である。 (C) Internal pressure of thepackage 5 If air remains in the gap 43 in the titanium package 5, the titanium material 7 is oxidized and nitrided during heating before hot working, and the titanium composite material to be manufactured The ductility of 1 decreases. For this reason, it is effective to depressurize the inside of the titanium packing body 5 to make a high vacuum.
チタン梱包体５内の空隙４３に空気が残存していると、熱間加工前の加熱時にチタン材７が酸化・窒化してしまい、製造されるチタン複合材１の延性が低下する。このため、チタン梱包体５内を減圧して高真空とすることが有効である。 (C) Internal pressure of the
熱間加工時のチタン材７の酸化・窒化を防止するためには、チタン梱包体５の内部圧力（絶対圧）を１０Ｐａ以下、好ましくは１Ｐａ以下にすることがよい。チタン梱包体５の内部圧力が１０Ｐａより大きいと、残留している空気によりチタン材７が酸化、または窒化してしまう。内部圧力を極端に小さくすることは、装置の気密性向上、および真空排気装置の増強などを要し、製造コストの増大に繋がるので、内部圧力の下限は、１×１０－３Ｐａとするのがよい。
In order to prevent oxidation / nitridation of the titanium material 7 during hot working, the internal pressure (absolute pressure) of the titanium package 5 should be 10 Pa or less, preferably 1 Pa or less. When the internal pressure of the titanium package 5 is greater than 10 Pa, the titanium material 7 is oxidized or nitrided by the remaining air. Making the internal pressure extremely small requires improvement of the airtightness of the device and enhancement of the vacuum exhaust device, etc., leading to an increase in manufacturing cost. Therefore, the lower limit of the internal pressure is set to 1 × 10 −3 Pa. Is good.
３．チタン複合材１の製造方法
チタン複合材１は、チタン梱包体５に熱間加工、またはさらに冷間加工を行うことにより製造される。 3. Method for ProducingTitanium Composite Material 1 The titanium composite material 1 is produced by subjecting the titanium package 5 to hot working or further cold working.
チタン複合材１は、チタン梱包体５に熱間加工、またはさらに冷間加工を行うことにより製造される。 3. Method for Producing
（ａ）熱間加工方法
熱間加工の方法は、製品の形状によって選択することができる。板材のチタン複合材１を製造する場合は、直方体形状（スラブ）のチタン梱包体５を加熱して、熱間圧延を行い、チタン板とする。必要に応じて、従来工程と同様に、熱間圧延後に表面の酸化層を酸洗などで除去した後、冷間圧延を行い、さらに薄く加工してもよい。 (A) Hot working method The hot working method can be selected according to the shape of the product. When manufacturing thetitanium composite material 1 of a plate material, the rectangular parallelepiped (slab) titanium package 5 is heated and hot-rolled to obtain a titanium plate. If necessary, after the hot rolling, the surface oxide layer may be removed by pickling or the like after hot rolling, and then cold rolling may be performed to further reduce the thickness.
熱間加工の方法は、製品の形状によって選択することができる。板材のチタン複合材１を製造する場合は、直方体形状（スラブ）のチタン梱包体５を加熱して、熱間圧延を行い、チタン板とする。必要に応じて、従来工程と同様に、熱間圧延後に表面の酸化層を酸洗などで除去した後、冷間圧延を行い、さらに薄く加工してもよい。 (A) Hot working method The hot working method can be selected according to the shape of the product. When manufacturing the
丸棒や線材のチタン複合材１を製造する場合は、円柱や多角形形状（ビレット）のチタン梱包体５を加熱して、熱間圧延や熱間押し出しを行い、チタン丸棒や線材とする。また、必要に応じて、従来工程と同様に、熱間加工後に酸化層を酸洗などで除去した後、冷間圧延を行い、さらに細く加工してもよい。
When manufacturing the titanium composite material 1 of a round bar or wire, the cylindrical packing or polygonal (billet) titanium packing body 5 is heated and hot rolled or hot extruded to obtain a titanium round bar or wire. . Further, as necessary, after the hot working, the oxide layer may be removed by pickling or the like, and then cold-rolled and further thinned as in the conventional process.
（ａ－１）熱間加工の加熱温度
さらに、押出形材のチタン複合材１を製造する場合は、円柱や多角形形状（ビレット）のチタン梱包体５を加熱して、熱間押出を行い、種々の断面形状のチタン形材とする。熱間加工前の加熱温度としては、通常のチタンスラブやビレットを熱間加工する場合と同様の加熱温度とすればよい。加熱温度は、チタン梱包体５の大きさや熱間加工の度合い（加工率）によって異なるが、６００℃以上１２００℃以下に加熱することが好ましい。 (A-1) Heating temperature for hot working Further, when manufacturing the extrudedtitanium composite material 1, the cylindrical packing or polygonal (billet) titanium package 5 is heated to perform hot extrusion. Titanium profiles with various cross-sectional shapes are used. The heating temperature before hot working may be the same as that used when hot working a normal titanium slab or billet. The heating temperature varies depending on the size of the titanium package 5 and the degree of hot working (working rate), but it is preferable to heat to 600 ° C. or more and 1200 ° C. or less.
さらに、押出形材のチタン複合材１を製造する場合は、円柱や多角形形状（ビレット）のチタン梱包体５を加熱して、熱間押出を行い、種々の断面形状のチタン形材とする。熱間加工前の加熱温度としては、通常のチタンスラブやビレットを熱間加工する場合と同様の加熱温度とすればよい。加熱温度は、チタン梱包体５の大きさや熱間加工の度合い（加工率）によって異なるが、６００℃以上１２００℃以下に加熱することが好ましい。 (A-1) Heating temperature for hot working Further, when manufacturing the extruded
加熱温度が低過ぎると、チタン梱包体５の高温強度が高く、変形能が低いため、熱間加工中に割れが発生し易い。特に、チタン梱包体５の溶接部が割れて、内部が露出して一部が脱落したり、内部が酸化したりすると、チタン複合材１に必要な特性が得られなくなる。また、チタン化合物の粒の周囲にある構成元素の拡散層が形成されず、内層部のチタン化合物の粒とチタンが十分に結合できない。このため、チタン複合材を加工する際にチタン化合物を起点に割れが発生する場合がある。一方、加熱温度が高過ぎると、得られたチタン複合材１の組織が粗くなり、十分な材料特性が得られない。また、酸化により表面の梱包材６が減肉されてしまう。よって、加熱温度は、６００℃～１２００℃とすることが推奨される。
If the heating temperature is too low, the high temperature strength of the titanium package 5 is high and the deformability is low, so that cracking is likely to occur during hot working. In particular, if the welded portion of the titanium package 5 is cracked and the inside is exposed and partly falls off or the inside is oxidized, the characteristics necessary for the titanium composite 1 cannot be obtained. Further, the diffusion layer of the constituent elements around the titanium compound grains is not formed, and the titanium compound grains and titanium in the inner layer portion cannot be sufficiently bonded. For this reason, when processing a titanium composite material, a crack may generate | occur | produce from a titanium compound. On the other hand, when the heating temperature is too high, the structure of the obtained titanium composite 1 becomes rough, and sufficient material properties cannot be obtained. Further, the packing material 6 on the surface is thinned by oxidation. Therefore, it is recommended that the heating temperature be 600 ° C. to 1200 ° C.
（ａ－２）熱間加工の加工率
熱間加工の際の加工の度合い、すなわち加工率は、チタン複合材１の内層部４の空隙率を制御するために選択することができる。ここでいう加工率は、チタン梱包体５の断面積と熱間加工後のチタン複合材１の断面積の差を、チタン梱包体５の断面積で除した割合（百分率）である。 (A-2) Hot working rate The degree of hot working, ie, the working rate, can be selected to control the porosity of theinner layer portion 4 of the titanium composite 1. The processing rate here is a ratio (percentage) obtained by dividing the difference between the cross-sectional area of the titanium package 5 and the cross-sectional area of the titanium composite 1 after hot working by the cross-sectional area of the titanium package 5.
熱間加工の際の加工の度合い、すなわち加工率は、チタン複合材１の内層部４の空隙率を制御するために選択することができる。ここでいう加工率は、チタン梱包体５の断面積と熱間加工後のチタン複合材１の断面積の差を、チタン梱包体５の断面積で除した割合（百分率）である。 (A-2) Hot working rate The degree of hot working, ie, the working rate, can be selected to control the porosity of the
この加工率が低い場合には、チタン梱包体５内部の空隙４３が十分に圧着されないため、熱間加工後であっても、空隙４３のまま残存する。このような空隙を多く含むチタン複合材１は、含有する空隙の分だけ軽量となり、機械的特性向上効果にも問題はない。ただし、内層部４に存在する空隙４３が多いため、機械的特性が十分に得られない。一方、加工率が増大すると、空隙率は低下して機械的特性が向上する。このため、製造されるチタン複合材１の機械的特性が重要視される場合には、加工率は高いほうが好ましい。
When the processing rate is low, the gap 43 inside the titanium package 5 is not sufficiently crimped, so that the gap 43 remains even after hot working. The titanium composite material 1 containing a large amount of voids is lighter by the amount of voids contained, and there is no problem in the effect of improving mechanical properties. However, since there are many voids 43 present in the inner layer portion 4, sufficient mechanical properties cannot be obtained. On the other hand, when the processing rate is increased, the porosity is decreased and the mechanical properties are improved. For this reason, when the mechanical characteristics of the titanium composite material 1 to be manufactured are regarded as important, it is preferable that the processing rate is high.
（ｂ）熱間加工の工程
熱間圧延後は、焼鈍、冷間圧延に供してもよい。チタン複合材１は、熱間加工材（例えば熱延板）でも、冷間加工材（例えば冷延板）でも、機械的特性向上効果に大きな違いはない。また、表面状態も圧延まま、酸洗仕上げ、焼鈍仕上げのいずれの状態でも良く、機械的特性向上効果は変わらない。 (B) Step of hot working After hot rolling, it may be subjected to annealing and cold rolling. Thetitanium composite material 1 has no significant difference in the effect of improving the mechanical properties, whether it is a hot-worked material (for example, hot-rolled plate) or a cold-worked material (for example, cold-rolled plate). Further, the surface state may be any state of rolling, pickling finish and annealing finish, and the effect of improving mechanical properties is not changed.
熱間圧延後は、焼鈍、冷間圧延に供してもよい。チタン複合材１は、熱間加工材（例えば熱延板）でも、冷間加工材（例えば冷延板）でも、機械的特性向上効果に大きな違いはない。また、表面状態も圧延まま、酸洗仕上げ、焼鈍仕上げのいずれの状態でも良く、機械的特性向上効果は変わらない。 (B) Step of hot working After hot rolling, it may be subjected to annealing and cold rolling. The
４．チタン梱包体５の製造方法
（ａ）充填材７，８の混合
チタン材７にチタン化合物等の粉末８を均一かつ高密度で充填する必要がある。このためには、これらのチタン材７およびチタン化合物等の粉末８を容器に充填して回転または振動させて、内部のチタン材７、およびチタン化合物等の粉末８が均一に分散するように混合すればよい。 4). Manufacturing method of titanium package 5 (a) Mixing of fillers 7 and 8 The titanium material 7 needs to be uniformly and densely filled with powder 8 such as a titanium compound. For this purpose, these titanium material 7 and titanium compound powder 8 are filled in a container and rotated or vibrated, and mixed so that the internal titanium material 7 and titanium compound powder 8 are uniformly dispersed. do it.
（ａ）充填材７，８の混合
チタン材７にチタン化合物等の粉末８を均一かつ高密度で充填する必要がある。このためには、これらのチタン材７およびチタン化合物等の粉末８を容器に充填して回転または振動させて、内部のチタン材７、およびチタン化合物等の粉末８が均一に分散するように混合すればよい。 4). Manufacturing method of titanium package 5 (a) Mixing of
撹拌する方法は、容器を上下方向に回転させる、水平から２０～７０°傾けて斜め方向に回転させる、容器を上下方向や水平方向等に振動させる、あるいは容器内に撹拌子を挿入して撹拌子を回転させたりする方法等が挙げられる。
Stirring can be done by rotating the container up and down, tilting it 20 to 70 ° from the horizontal and rotating it in an oblique direction, vibrating the container in the vertical and horizontal directions, or inserting a stirring bar into the container and stirring. Examples include a method of rotating the child.
撹拌時間は、容器の大きさや混合するチタン材７、およびチタン化合物等の粉末８の量により変化するが、１～３０分間であるのが好ましい。生産性を考慮すると、数分間で均一に混合できるように、容器の大きさや処理量を決めることが好ましい。
The stirring time varies depending on the size of the container and the amount of the titanium material 7 to be mixed and the powder 8 of the titanium compound or the like, but is preferably 1 to 30 minutes. In consideration of productivity, it is preferable to determine the size of the container and the processing amount so that the mixture can be uniformly mixed within a few minutes.
混合したチタン材７とチタン化合物等の粉末８は、そのままでチタン梱包体５内に充填する。あるいは、チタン材７のハンドリング性向上やこれら空隙を少なくするために、圧縮成形して図５に示すようなチタンブリケット１０としてから、チタン梱包体５内に格納してもよい。
The mixed titanium material 7 and powder 8 such as titanium compound are filled in the titanium package 5 as they are. Alternatively, in order to improve the handleability of the titanium material 7 and reduce these gaps, the titanium briquette 10 as shown in FIG.
（ｂ）溶接
チタン梱包材６を溶接部１１で溶接する方法には、ＴＩＧ溶接またはＭＩＧ溶接等のアーク溶接、ならびに電子ビーム溶接やレーザー溶接等が例示され、特に限定はされない。ただし、溶接雰囲気は、チタン材７、およびチタン梱包材６の面が酸化、または窒化されないように、真空雰囲気あるいは不活性ガス雰囲気で溶接を行うことが好ましい。 (B) Welding The method of welding thetitanium packing material 6 with the welded portion 11 includes arc welding such as TIG welding or MIG welding, electron beam welding, laser welding, and the like, and is not particularly limited. However, it is preferable that welding is performed in a vacuum atmosphere or an inert gas atmosphere so that the surfaces of the titanium material 7 and the titanium packing material 6 are not oxidized or nitrided.
チタン梱包材６を溶接部１１で溶接する方法には、ＴＩＧ溶接またはＭＩＧ溶接等のアーク溶接、ならびに電子ビーム溶接やレーザー溶接等が例示され、特に限定はされない。ただし、溶接雰囲気は、チタン材７、およびチタン梱包材６の面が酸化、または窒化されないように、真空雰囲気あるいは不活性ガス雰囲気で溶接を行うことが好ましい。 (B) Welding The method of welding the
チタン梱包材６のつなぎ目（溶接部１１）を最後に溶接する際には、チタン梱包体５を真空雰囲気の容器（チャンバー）に入れて溶接を行い、チタン梱包体５の内部を真空に保つことが好ましい。
When welding the joint (welded portion 11) of the titanium packing material 6 lastly, the titanium packing body 5 is put in a vacuum atmosphere container (chamber) and welded to keep the inside of the titanium packing body 5 in a vacuum. Is preferred.
図６に示すように、チタン化合物等の粉末８と混合し圧縮成形したチタンブリケット１０を梱包材であるチタン展伸材で覆い、チタン展伸材の全周囲をシーム溶接（回転電極を用いた抵抗溶接）して密閉し、チタン梱包体１２を製造してもよい。この際、事前に端部に穴をあけて銅管をろう溶接した銅管を通して、チタン展伸材の内部を所定の圧力になるまで減圧し、減圧後に銅管を圧着して、チタン展伸材内部の圧力を保ってもよい。
As shown in FIG. 6, a titanium briquette 10 mixed with a powder 8 such as a titanium compound and compression-molded is covered with a titanium expanded material as a packing material, and the entire circumference of the titanium expanded material is seam welded (using a rotating electrode). The titanium package 12 may be manufactured by sealing with resistance welding. At this time, the inside of the titanium wrought material is depressurized to a predetermined pressure through a copper pipe in which a hole is drilled at the end in advance and the copper pipe is solder-welded. The pressure inside the material may be maintained.
５．チタン複合材１の用途
高い引張強度と良好な加工性を有するとともに、低コストで製造可能であることから、自動車などの陸上輸送機器の構造部材として用いることができる。 5. Use oftitanium composite 1 Since it has high tensile strength and good workability and can be manufactured at low cost, it can be used as a structural member for land transportation equipment such as automobiles.
高い引張強度と良好な加工性を有するとともに、低コストで製造可能であることから、自動車などの陸上輸送機器の構造部材として用いることができる。 5. Use of
表１に示すチタン梱包体を製造し、このチタン梱包体に表１に示す製作工程でチタン複合材１（板材）を製造した。
A titanium package shown in Table 1 was produced, and a titanium composite 1 (plate material) was produced in the production process shown in Table 1 on the titanium package.
充填材として、クロール法により製造した粒度が２．５ｍｍ以上６ｍｍ以下であり、化学組成がＪＩＳ１種相当（Ｃ：０．００２％、Ｈ：０．００１％、Ｏ：０．０３％、Ｎ：０．００１％、Ｆｅ：０．０３％、残部Ｔｉおよび不純物）のスポンジチタンを用いた。また、充填材として、市販のＴｉＯ２粉末（平均粒径２μｍ）、ＴｉＣ粉末（平均粒径３μｍ）またはＴｉＮ粉末（平均粒径５μｍ）を用いた。
As a filler, the particle size produced by the crawl method is 2.5 mm or more and 6 mm or less, and the chemical composition is equivalent to JIS class 1 (C: 0.002%, H: 0.001%, O: 0.03%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) were used. As the filler, commercially available TiO 2 powder (average particle size 2 μm), TiC powder (average particle size 3 μm) or TiN powder (average particle size 5 μm) was used.
上記のスポンジチタンと、チタン化合物等の粉末は、Ｖ型混合器に所定量を投入して混合した。混合した素材は、金型に投入して圧縮成形し、厚さ１５ｍｍ、幅５０ｍｍ、長さ６０ｍｍの図５に示すチタンブリケットにした。比較として、試料Ｎｏ．１１では、スポンジチタン粒７のみ添加し、粉末原料８を添加しないでチタンブリケットを作成した。
The above-mentioned sponge titanium and powders of titanium compound and the like were mixed by feeding a predetermined amount into a V-type mixer. The mixed material was put into a mold and compression molded to form a titanium briquette shown in FIG. 5 having a thickness of 15 mm, a width of 50 mm, and a length of 60 mm. For comparison, Sample No. In No. 11, only titanium titanium particles 7 were added, and titanium briquette was prepared without adding the powder raw material 8.
チタン梱包材として、ＪＩＳ１種（ＴＰ２７０Ｃ；Ｃ：０．００１％、Ｈ：０．００５％、Ｏ：０．０４％、Ｎ：０．００１％、Ｆｅ：０．０３％、残部Ｔｉおよび不純物）またはＪＩＳ２種（ＴＰ３４０Ｃ；Ｃ：０．００２％、Ｈ：０．００４％、Ｏ：０．０９％、Ｎ：０．００１％、Ｆｅ：０．０５％、残部Ｔｉおよび不純物）工業用純チタン材からなる、厚さ１．０ｍｍの薄板を用いた。
As a titanium packing material, JIS type 1 (TP270C; C: 0.001%, H: 0.005%, O: 0.04%, N: 0.001%, Fe: 0.03%, balance Ti and impurities) Or JIS type 2 (TP340C; C: 0.002%, H: 0.004%, O: 0.09%, N: 0.001%, Fe: 0.05%, balance Ti and impurities) industrial pure titanium A thin plate made of a material and having a thickness of 1.0 mm was used.
図６に示すように、チタンブリケットを梱包材である工業用純チタン材で覆い、工業用純チタン材の全周囲をシーム溶接（回転電極を用いた抵抗溶接）して密閉した。この工業用純チタン材は、事前に端部に穴をあけて銅管をろう溶接した。シーム溶接後、銅管を通して、工業用純チタン材の内部を所定の圧力（０．０６～１．２Ｐａ）になるまで減圧し、減圧後に銅管を圧着して、工業用純チタン材内部の圧力を保った。試料Ｎｏ．１２では３８Ｐａまで減圧したところで、銅管を圧着して梱包体とした。
As shown in FIG. 6, the titanium briquette was covered with an industrial pure titanium material as a packing material, and the entire circumference of the industrial pure titanium material was sealed by seam welding (resistance welding using a rotating electrode). This pure titanium material for industrial use was previously welded to a copper tube by making a hole in the end. After seam welding, the pressure inside the industrial pure titanium material is reduced to a predetermined pressure (0.06 to 1.2 Pa) through the copper tube. The pressure was maintained. Sample No. 12, when the pressure was reduced to 38 Pa, a copper tube was pressure-bonded to form a package.
作製したチタン梱包体は、大気雰囲気下、８５０℃で４時間加熱した後、熱間圧延を行い、厚さ２．０ｍｍのチタン複合材を製作した。チタン複合材は、７２５℃で１５分間焼鈍後、酸洗して表層のスケールを除去して、組織観察や引張試験に供した。
The produced titanium package was heated at 850 ° C. for 4 hours in an air atmosphere and then hot-rolled to produce a 2.0 mm-thick titanium composite. The titanium composite was annealed at 725 ° C. for 15 minutes, then pickled to remove the scale of the surface layer, and subjected to a structure observation and a tensile test.
チタン複合材の長さ方向（圧延方向）および厚さ方向に平行な断面（厚さ断面）が観察できるように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観察面を研磨し（鏡面化仕上げ）、観察用試料に仕上げた。空隙率は、光学顕微鏡で、上記観察用試料の厚さ中心部を２０か所写真撮影して、個々の写真毎に空隙の面積率を測定してそれらの平均値を求めた。筋状化合物集合体は、光学顕微鏡で、上記観察用試料の厚さ中心部を観察して、その形態を求めた。また、観察された筋状化合物集合体２０個について、厚さｔと長さＬを測定してＬ／ｔを算出して、それらの平均値を求めた。
After embedding in the resin so that a cross section (thickness cross section) parallel to the length direction (rolling direction) and thickness direction of the titanium composite can be observed, the observation surface is polished with diamond or alumina suspension ( Mirror finish) and finished the sample for observation. The porosity was obtained by taking 20 photographs of the central portion of the thickness of the observation sample with an optical microscope, measuring the area ratio of the void for each individual photograph, and obtaining the average value thereof. The shape of the streak-like compound aggregate was determined by observing the central portion of the thickness of the observation sample with an optical microscope. Moreover, about 20 observed streak compound aggregates, thickness t and length L were measured, L / t was calculated, and those average values were calculated | required.
拡散層の厚さは、ＴｉＯ２粉末、ＴｉＣ粉末，ＴｉＮ粉末を添加したＮｏ．２、Ｎｏ．４、Ｎｏ．６について、上記観察用試料の厚さ中心部に観察された筋状化合物集合体５個について、その中に観察された３個のチタン化合物の粒をＥＰＭＡで測定した。チタン化合物の粒が中心になるようにして厚さ方向に線分析を行い、内層部のチタンの値を基準にして、それよりもチタン化合物の構成元素（炭素、窒素または酸素）濃度が高く、粒子を除いた片側の領域の距離を測定して、それらを平均して、筋状化合物集合体それぞれの拡散層の厚さとして求めた。
The thickness of the diffusion layer is No. 1 to which TiO 2 powder, TiC powder and TiN powder were added. 2, No. 4, no. As for No. 6, the five titanium compound grains observed in the central portion of the thickness of the observation sample were measured with EPMA for the three titanium compound grains observed therein. Perform line analysis in the thickness direction so that the grains of the titanium compound are in the center, and based on the value of titanium in the inner layer, the concentration of the constituent elements (carbon, nitrogen or oxygen) of the titanium compound is higher than that, The distance of the area | region of the one side except particle | grains was measured, they were averaged, and it calculated | required as thickness of each diffusion layer of a streak compound aggregate.
引張試験はチタン複合材の圧延方向で評価した。引張速度は、降伏点を超えるまで０．４％／分で、降伏点を超えてからは３０％／分で行い、強度を測定した。また、降伏するまでの応力－ひずみ曲線の勾配からヤング率を求めた。
The tensile test was evaluated in the rolling direction of the titanium composite material. The tensile rate was 0.4% / min until exceeding the yield point, and 30% / min after exceeding the yield point, and the strength was measured. The Young's modulus was obtained from the slope of the stress-strain curve until yielding.
結果を表１にまとめて示す。
The results are summarized in Table 1.
図７は、Ｔｉ－０．１％Ｎ板の断面ミクロ組織の写真の一例である。
FIG. 7 is an example of a photograph of a cross-sectional microstructure of a Ti-0.1% N plate.
図７に例示するように、本発明例である試料Ｎｏ．８のチタン複合板の断面の組織を観察すると、黒く見えるチタン化合物が所々に認められる。この黒い筋状化合物集合体は、窒化チタンの集合体であり、Ｘ線回折で測定した結果、ＴｉＮであった。
As illustrated in FIG. 7, sample no. When the structure of the cross section of the titanium composite plate of No. 8 is observed, titanium compounds that appear black are recognized in some places. This black streak-like compound aggregate was an aggregate of titanium nitride, and as a result of measurement by X-ray diffraction, it was TiN.
チタンに、炭化物、窒化物および酸化物から選択される１種以上のチタン化合物が分散している本発明例の試料Ｎｏ．１～８は、これらのチタン化合物を有していない試料Ｎｏ．１０に比べて、チタン複合材の強度やヤング率が向上した。なお、チタン梱包体５を作製する際に、チタン梱包体の内部の真空度を１０Ｐａより大きくした試料Ｎｏ．９は、チタン複合材の内部が一部で酸化し、強度は低下したものの、ヤング率は一定値以上を維持していた。ＴｉＯ２粉末を添加したＮｏ．２では、酸素の拡散層の厚さが４～６μｍであった。ＴｉＣ粉末を添加したＮｏ．４では、炭素の拡散層の厚さが２５～３２μｍであった。ＴｉＮ粉末を添加したＮｏ．６では、窒素の拡散層の厚さが１～２μｍであった。
Sample No. of the present invention example in which one or more titanium compounds selected from carbides, nitrides and oxides are dispersed in titanium. Samples Nos. 1 to 8 have no titanium compound. Compared to 10, the strength and Young's modulus of the titanium composite were improved. Note that when the titanium package 5 was manufactured, the sample No. 1 with the degree of vacuum inside the titanium package greater than 10 Pa was used. In No. 9, the inside of the titanium composite was partially oxidized and the strength decreased, but the Young's modulus was maintained at a certain value or more. No. with TiO 2 powder added. In No. 2, the thickness of the oxygen diffusion layer was 4 to 6 μm. No. to which TiC powder was added. In No. 4, the thickness of the carbon diffusion layer was 25 to 32 μm. No. with TiN powder added. In No. 6, the thickness of the nitrogen diffusion layer was 1-2 μm.
酸化物の粉末を多量に添加した試料Ｎｏ．１１では、熱間圧延時に内部割れが発生して、健全なチタン複合材が得られなかった。チタン梱包体５の圧下率が小さく、内層部の空隙率が大きくなった試料Ｎｏ．１２では、酸化物が空隙とともに方向性なく点在しており、引張試験片を製作する際に割れてしまった。
Sample No. with a large amount of oxide powder added. In No. 11, an internal crack occurred during hot rolling, and a healthy titanium composite material could not be obtained. Sample No. 2 in which the rolling reduction of the titanium package 5 was small and the porosity of the inner layer portion was large. In No. 12, the oxide was interspersed with the voids without directionality, and cracked when the tensile test piece was manufactured.
表２に示すように、チタン梱包体からチタン複合材を製造した。
As shown in Table 2, a titanium composite material was manufactured from a titanium package.
充填材として使用するスポンジチタンは、クロール法により製造した化学組成がＪＩＳ１種相当（Ｃ：０．００１％、Ｈ：０．００１％、Ｏ：０．０４％、Ｎ：０．００１％、Ｆｅ：０．０３％、残部Ｔｉおよび不純物）のスポンジチタンで、スポンジチタンＢは粒度が６ｍｍ以上１３ｍｍ以下ものを、スポンジチタンＣは粒度が２．５ｍｍ以上６ｍｍ以下のものを、スポンジチタンＤは粒度が０．８ｍｍ以上２．５ｍｍ以下のものを、それぞれ用いた。
Sponge titanium used as a filler has a chemical composition produced by the crawl method equivalent to JIS class 1 (C: 0.001%, H: 0.001%, O: 0.04%, N: 0.001%, Fe : 0.03%, balance Ti and impurities), sponge titanium B has a particle size of 6 mm to 13 mm, sponge titanium C has a particle size of 2.5 mm to 6 mm, and sponge titanium D has a particle size of Each having a thickness of 0.8 mm to 2.5 mm.
また、チタンスクラップとして、ＪＩＳ２種（Ｃ：０．００２％、Ｈ：０．００６％、Ｏ：０．０８％、Ｎ：０．００１％、Ｆｅ：０．０５％、残部Ｔｉおよび不純物）の薄板を１０～２０ｍｍ角に切断したものを一部（試料Ｎｏ．２６，２７）で使用した。
さらに、充填材として使用するチタン化合物等の粉末は、市販のＴｉＯ２粉末（平均粒径２μｍ）、ＴｉＣ粉末（平均粒径３μｍ）またはＴｉＮ粉末（平均粒径５μｍ）を用いた。これらのスポンジチタン粒とチタン化合物等の粉末は、Ｖ型混合器に所定量を投入して混合した。 Moreover, as titanium scrap,JIS 2 types (C: 0.002%, H: 0.006%, O: 0.08%, N: 0.001%, Fe: 0.05%, balance Ti and impurities) A thin plate cut into 10 to 20 mm square was used in part (sample Nos. 26 and 27).
Further, as the powder of titanium compound or the like used as the filler, a commercially available TiO 2 powder (average particle size 2 μm), TiC powder (average particle size 3 μm) or TiN powder (average particle size 5 μm) was used. A predetermined amount of these sponge titanium particles and titanium compound powder were mixed in a V-type mixer.
さらに、充填材として使用するチタン化合物等の粉末は、市販のＴｉＯ２粉末（平均粒径２μｍ）、ＴｉＣ粉末（平均粒径３μｍ）またはＴｉＮ粉末（平均粒径５μｍ）を用いた。これらのスポンジチタン粒とチタン化合物等の粉末は、Ｖ型混合器に所定量を投入して混合した。 Moreover, as titanium scrap,
Further, as the powder of titanium compound or the like used as the filler, a commercially available TiO 2 powder (
梱包材の素材として、工業用純チタン材は、ＪＩＳ１種（ＴＰ２７０ＨＣ：０．００２％、Ｈ：０．００６％、Ｏ：０．０４％、Ｎ：０．００２％、Ｆｅ：０．０３％、残部Ｔｉおよび不純物）、ＪＩＳ２種（ＴＰ３４０Ｈ；Ｃ：０．００１％、Ｈ：０．００２％、Ｏ：０．１０％、Ｎ：０．００２％、Ｆｅ：０．０６％、残部Ｔｉおよび不純物）、およびＴｉ－０．０６％Ｐｄの酸洗した厚さ１０ｍｍの厚板を用いた。
As a packaging material, industrial pure titanium material is JIS type 1 (TP270HC: 0.002%, H: 0.006%, O: 0.04%, N: 0.002%, Fe: 0.03%) , Balance Ti and impurities), JIS type 2 (TP340H; C: 0.001%, H: 0.002%, O: 0.10%, N: 0.002%, Fe: 0.06%, balance Ti and Impurities), and a 10 mm thick plate washed with Ti-0.06% Pd.
図４に示すように、工業用純チタン材の５枚を仮組みし、ここにスポンジチタン粒、あるいはチタンスクラップとチタン化合物等の粉末の混合物（充填材）を充填して、残りの工業用純チタン材であるチタン梱包材で蓋をした。
As shown in FIG. 4, five industrial pure titanium materials are temporarily assembled and filled with sponge titanium particles or a mixture of titanium scrap and titanium compound powder (filler), and the remaining industrial titanium The lid was covered with a titanium packing material which is a pure titanium material.
この状態で、真空チャンバー内に入れて、所定の圧力になるまで減圧（真空）した後、梱包材の継ぎ目を全周電子ビームで溶接した。この時のチャンバー内の圧力は、９．５×１０－３～２．１×１０－１Ｐａであった。
In this state, after putting in a vacuum chamber and reducing the pressure (vacuum) until a predetermined pressure was reached, the seam of the packing material was welded with an all-around electron beam. The pressure in the chamber at this time was 9.5 × 10 −3 to 2.1 × 10 −1 Pa.
以上のようにして、内部にスポンジチタンやチタンスクラップとチタン化合物等の粉末の混合物を充填し、雰囲気が真空であるチタン梱包体を用意した。チタン梱包体の大きさは、厚さ８０×幅１００×長さ１２０ｍｍとした。
As described above, a titanium packing body was prepared in which the inside was filled with a mixture of titanium sponge, titanium scrap, and a powder of a titanium compound, and the atmosphere was vacuum. The size of the titanium package was 80 x thickness 100 x length 120 mm.
作製したチタン梱包体は、大気雰囲気下、８５０℃で６時間加熱した後、熱間圧延を行い、厚さ５ｍｍのチタン複合板を製作した。その後、チタン複合材は、７２５℃で１５分間焼鈍後、酸洗して表層のスケールを除去して引張試験に供した。実施例１と同様に組織観察や引張試験を行ない、チタン複合材の空隙率、チタン化合物の形態や大きさＬ／ｔ、拡散層の厚さ、強度およびヤング率を求めた。
The produced titanium package was heated at 850 ° C. for 6 hours in an air atmosphere, and then hot-rolled to produce a titanium composite plate having a thickness of 5 mm. Thereafter, the titanium composite was annealed at 725 ° C. for 15 minutes, and then pickled to remove the scale of the surface layer and subjected to a tensile test. The structure observation and the tensile test were performed in the same manner as in Example 1, and the porosity of the titanium composite material, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer were determined.
結果を表２にまとめて示す。
The results are summarized in Table 2.
梱包材にＪＩＳ２種を用いた場合、チタン化合物粉末を添加した本発明例である試料Ｎｏ．１３～１９は、チタン化合物を添加していない試料Ｎｏ．２０に比べて、チタン複合材の強度やヤング率が向上した。
When JIS type 2 is used for the packing material, sample No. which is an example of the present invention to which titanium compound powder is added. Samples Nos. 13 to 19 are sample Nos. To which no titanium compound was added. Compared to 20, the strength and Young's modulus of the titanium composite were improved.
また、チタン梱包体の圧下率が小さく、内層部の空隙率が大きくなった試料Ｎｏ．２１では、酸化物が空隙とともに方向性なく点在しており、引張試験片を製作する際に割れてしまった。
Specimen No. with a reduced rolling ratio of the titanium package and a larger porosity of the inner layer portion. In No. 21, the oxide was interspersed with voids without directionality, and cracked when the tensile test piece was manufactured.
梱包材にＪＩＳ１種を用いた場合、チタン化合物粉末を添加した本発明例である試料Ｎｏ．２２～２４は、チタン化合物を添加していない試料Ｎｏ．２５に比べて、チタン複合材の強度やヤング率が向上した。
When JIS Class 1 is used for the packing material, Sample No. which is an example of the present invention to which titanium compound powder is added. Nos. 22 to 24 are sample Nos. To which no titanium compound was added. Compared to 25, the strength and Young's modulus of the titanium composite were improved.
充填材に酸素量が０．０８質量％の薄板スクラップを用いた場合、チタン化合物粉末を添加した本発明例である試料Ｎｏ．２６は、チタン化合物粉末を添加していない試料Ｎｏ．２７に比べて、チタン複合材１の強度やヤング率が向上した。
When using thin sheet scraps with an oxygen content of 0.08% by mass for the filler, Sample No. Sample No. 26 to which no titanium compound powder was added. Compared to 27, the strength and Young's modulus of the titanium composite 1 were improved.
梱包材にＪＩＳ１種を用いた場合は、ＪＩＳ２種を用いた梱包材に比べて、加工性のよいチタン複合材１が得られる。梱包材６にＴｉ－０．０６％Ｐｄを用いた試料Ｎｏ．２３は、ＪＩＳ２種を用いた梱包材６に比べて、耐食性のよいチタン複合材が得られる。なお、ＴｉＯ２粉末を添加したＮｏ．１４では、酸素の拡散層の厚さは２～６μｍであった。ＴｉＣ粉末を添加したＮｏ．１６では、炭素の拡散層の厚さは１２～１８μｍであった。ＴｉＮ粉末を添加したＮｏ．１７では、窒素の拡散層の厚さは１～２μｍであった。
When JIS type 1 is used for the packaging material, the titanium composite material 1 with good workability is obtained as compared with the packaging material using JIS type 2. Sample No. 6 using Ti-0.06% Pd as the packing material 6 was used. No. 23 is a titanium composite material with better corrosion resistance than the packaging material 6 using JIS type 2. In addition, No. to which TiO 2 powder was added. 14, the thickness of the oxygen diffusion layer was 2 to 6 μm. No. to which TiC powder was added. In No. 16, the thickness of the carbon diffusion layer was 12 to 18 μm. No. with TiN powder added. In No. 17, the thickness of the nitrogen diffusion layer was 1-2 μm.
熱間圧延で得られた表２に示す、厚さ５ｍｍのチタン複合材である試料Ｎｏ．１３、１４、１６、２０を、７２５℃で１５分間焼鈍後、酸洗して表層のスケールを除去した。スケールを除去したチタン複合（熱間圧延材）は、１．０ｍｍの厚さまで冷間圧延を行い、その後、真空加熱炉を用いて７００℃で１５分間焼鈍して引張試験に供した。実施例１と同様に組織観察や引張試験を行い、チタン複合材の空隙率、チタン化合物の形態や大きさＬ／ｔ、拡散層の厚さ、強度およびヤング率を求めた。
Sample No. 5 which is a titanium composite material having a thickness of 5 mm shown in Table 2 obtained by hot rolling. 13, 14, 16, and 20 were annealed at 725 ° C. for 15 minutes, and then pickled to remove scale on the surface layer. The titanium composite from which the scale was removed (hot-rolled material) was cold-rolled to a thickness of 1.0 mm, and then annealed at 700 ° C. for 15 minutes using a vacuum heating furnace and subjected to a tensile test. Microstructure observation and a tensile test were performed in the same manner as in Example 1 to determine the porosity of the titanium composite, the form and size L / t of the titanium compound, the thickness, strength, and Young's modulus of the diffusion layer.
結果を表３にまとめて示す。
The results are summarized in Table 3.
本発明例である試料Ｎｏ．２８～３０は、チタン化合物粉末を添加することにより、チタン化合物粉末を添加していない試料Ｎｏ．３１に比べて、チタン複合材の強度やヤング率が向上した。なお、ＴｉＯ２粉末を添加したＮｏ．２９では、酸素の拡散層の厚さは１～４μｍであった。ＴｉＣ粉末を添加したＮｏ．３０では、炭素の拡散層の厚さは２～６μｍであった。
Sample No. which is an example of the present invention. Samples Nos. 28 to 30 were prepared by adding the titanium compound powder, so that no sample no. Compared to 31, the strength and Young's modulus of the titanium composite were improved. In addition, No. to which TiO 2 powder was added. In No. 29, the thickness of the oxygen diffusion layer was 1 to 4 μm. No. to which TiC powder was added. In No. 30, the thickness of the carbon diffusion layer was 2 to 6 μm.
１ チタン複合材
２ 表層部
３ 表層部
４ 内層部
４１ チタン
４２ チタン化合物
４２ａ 筋状化合物集合体
４３ 空隙
５ チタン梱包体
６ チタン梱包材
７ スポンジチタン
８ チタン化合物等の粉末
９ 空隙
１０ ブリケット
１１ 溶接部
１２ チタン梱包体
DESCRIPTION OFSYMBOLS 1 Titanium composite material 2 Surface layer part 3 Surface layer part 4 Inner layer part 41 Titanium 42 Titanium compound 42a Streaky compound aggregate 43 Cavity 5 Titanium packing body 6 Titanium packing material 7 Sponge titanium 8 Powders of titanium compound 9 Cavity 10 Briquette 11 Welding part 12 Titanium package
２ 表層部
３ 表層部
４ 内層部
４１ チタン
４２ チタン化合物
４２ａ 筋状化合物集合体
４３ 空隙
５ チタン梱包体
６ チタン梱包材
７ スポンジチタン
８ チタン化合物等の粉末
９ 空隙
１０ ブリケット
１１ 溶接部
１２ チタン梱包体
DESCRIPTION OF
Claims (6)
- 内層部と前記内層部を覆う表層部とを有するチタン複合材であって、
前記表層部は、ＪＩＳ１種～４種のいずれかに属する化学組成の工業用純チタン材またはチタン合金材からなり、
前記内層部は、チタンに、炭化物、窒化物および酸化物から選択される１種以上のチタン化合物が分散しており、前記炭化物の周囲に炭素が、前記窒化物の周囲に窒素が、前記酸化物の周囲に酸素が、それぞれが拡散した部分を備え、面積率で、０％超３０％以下の空隙を有する、
チタン複合材。 A titanium composite material having an inner layer portion and a surface layer portion covering the inner layer portion,
The surface layer portion is made of an industrial pure titanium material or a titanium alloy material having a chemical composition belonging to any one of JIS types 1 to 4,
In the inner layer portion, one or more kinds of titanium compounds selected from carbide, nitride and oxide are dispersed in titanium, carbon around the carbide, nitrogen around the nitride, and the oxidation Oxygen around each object has a portion where each diffuses, and the area ratio has voids of more than 0% and not more than 30%.
Titanium composite material. - 前記内層部は、炭素、窒素および酸素の平均含有量の合計が０．０５～２．０質量％であり、前記チタン化合物が圧延方向に並んだ筋状化合物集合体としてチタン材に分散している、
請求項１に記載のチタン複合材。 The inner layer portion has a total average content of carbon, nitrogen and oxygen of 0.05 to 2.0% by mass, and the titanium compound is dispersed in the titanium material as a streak compound aggregate arranged in the rolling direction. Yes,
The titanium composite according to claim 1. - 前記工業用純チタン材の化学組成は、質量％で、
Ｃ：０．０８％以下、
Ｈ：０．０１３％以下、
Ｏ：０．４％以下、
Ｎ：０．０５％以下、
Ｆｅ：０．５％以下、
残部：Ｔｉおよび不純物である、
請求項１または２に記載のチタン複合材。 The chemical composition of the industrial pure titanium material is mass%,
C: 0.08% or less,
H: 0.013% or less,
O: 0.4% or less,
N: 0.05% or less,
Fe: 0.5% or less,
Balance: Ti and impurities,
The titanium composite material according to claim 1 or 2. - ＪＩＳ１～４種のいずれかに属する工業用純チタン材またはチタン合金材からなるチタン梱包材に、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上と、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末と充填し、封入し、内部を１０Ｐａ以下に減圧することによりチタン梱包体とし、前記チタン梱包体に熱間加工を行う、
チタン複合材の製造方法。 One or more selected from sponge titanium, titanium briquette and titanium scrap, and carbon, carbides, nitrides and oxides, as a titanium packing material consisting of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4 Filling with one or more powders selected from the product, enclosing, and reducing the inside to 10 Pa or less to make a titanium package, hot processing the titanium package,
A method for producing a titanium composite material. - 前記熱間加工を行った後に冷間加工を行う、
請求項４に記載のチタン複合材の製造方法。 Cold working after the hot working,
The manufacturing method of the titanium composite material of Claim 4. - ＪＩＳ１～４種のいずれかに属する工業用純チタン材またはチタン合金材からなるチタン梱包材と、前記チタン梱包材の内部に充填された充填材とを備える梱包体であって、
前記充填材が、スポンジチタン、チタンブリケットおよびチタンスクラップから選択される１種以上と、炭素、炭化物、窒化物および酸化物から選択される１種以上の粉末とを有し、前記内部の圧力は１０Ｐａ以下である、
熱間加工用の梱包体。
A packing body comprising a titanium packing material made of industrial pure titanium material or titanium alloy material belonging to any one of JIS 1-4, and a filling material filled in the titanium packing material,
The filler has at least one selected from sponge titanium, titanium briquette and titanium scrap, and at least one powder selected from carbon, carbide, nitride and oxide, and the internal pressure is 10 Pa or less,
Package for hot working.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH042742A (en) * | 1990-04-19 | 1992-01-07 | Fuso Off Service:Kk | Composite titanium alloy, multilayered titanium material, titanium cutter and their manufacture |
| JPH0570805A (en) * | 1991-09-11 | 1993-03-23 | Osaka Titanium Co Ltd | Method for forming cuttings of high-melting-point active metal and its alloy |
| JP2000178671A (en) * | 1998-12-11 | 2000-06-27 | Sumitomo Sitix Amagasaki:Kk | Grain dispersed type titanium base composite material excellent in hot workability, its production and hot working method therefor |
| JP2012041583A (en) * | 2010-08-17 | 2012-03-01 | Sanyo Special Steel Co Ltd | Method for producing titanium product or titanium alloy product |
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- 2017-03-31 WO PCT/JP2017/013754 patent/WO2017171056A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH042742A (en) * | 1990-04-19 | 1992-01-07 | Fuso Off Service:Kk | Composite titanium alloy, multilayered titanium material, titanium cutter and their manufacture |
| JPH0570805A (en) * | 1991-09-11 | 1993-03-23 | Osaka Titanium Co Ltd | Method for forming cuttings of high-melting-point active metal and its alloy |
| JP2000178671A (en) * | 1998-12-11 | 2000-06-27 | Sumitomo Sitix Amagasaki:Kk | Grain dispersed type titanium base composite material excellent in hot workability, its production and hot working method therefor |
| JP2012041583A (en) * | 2010-08-17 | 2012-03-01 | Sanyo Special Steel Co Ltd | Method for producing titanium product or titanium alloy product |
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| JPWO2017171056A1 (en) | 2018-08-16 |
| JP6756363B2 (en) | 2020-09-16 |
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