TW201718119A - Titanium composite material, and titanium material for hot rolling - Google Patents
Titanium composite material, and titanium material for hot rolling Download PDFInfo
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- TW201718119A TW201718119A TW105124190A TW105124190A TW201718119A TW 201718119 A TW201718119 A TW 201718119A TW 105124190 A TW105124190 A TW 105124190A TW 105124190 A TW105124190 A TW 105124190A TW 201718119 A TW201718119 A TW 201718119A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 325
- 239000010936 titanium Substances 0.000 title claims abstract description 318
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 313
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims description 199
- 238000005098 hot rolling Methods 0.000 title claims description 90
- 239000002344 surface layer Substances 0.000 claims abstract description 158
- 239000010410 layer Substances 0.000 claims abstract description 143
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 210000001161 mammalian embryo Anatomy 0.000 claims description 73
- 238000005304 joining Methods 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 117
- 238000007254 oxidation reaction Methods 0.000 abstract description 117
- 238000010438 heat treatment Methods 0.000 description 101
- 238000000034 method Methods 0.000 description 50
- 239000000956 alloy Substances 0.000 description 43
- 229910045601 alloy Inorganic materials 0.000 description 39
- 238000002844 melting Methods 0.000 description 32
- 230000008018 melting Effects 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 31
- 238000010894 electron beam technology Methods 0.000 description 29
- 238000012360 testing method Methods 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000005275 alloying Methods 0.000 description 20
- 238000005096 rolling process Methods 0.000 description 19
- 239000011261 inert gas Substances 0.000 description 17
- 238000000137 annealing Methods 0.000 description 16
- 238000005097 cold rolling Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 238000005266 casting Methods 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 238000004453 electron probe microanalysis Methods 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000005253 cladding Methods 0.000 description 10
- 238000005554 pickling Methods 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- 238000005422 blasting Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011162 core material Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 206010040844 Skin exfoliation Diseases 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 210000002257 embryonic structure Anatomy 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000009703 powder rolling Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003584 silencer Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- B21B1/22—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 plates, strips, bands or sheets of indefinite length
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K15/00—Electron-beam welding or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/04—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a rolling mill
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Abstract
Description
本發明有關一種鈦複合材以及熱軋用鈦材。 The present invention relates to a titanium composite material and a titanium material for hot rolling.
鈦材於耐蝕性、耐氧化性、耐疲勞性、耐氫脆性、中子遮斷性等之特性方面堪稱良好。此等特性可藉由於鈦中添加各種合金元素而達成。 Titanium is excellent in properties such as corrosion resistance, oxidation resistance, fatigue resistance, hydrogen embrittlement resistance, and neutron blocking properties. These properties can be achieved by the addition of various alloying elements in the titanium.
鈦材料基於其優異之比強度及耐蝕性，在航空器領域之利用與日俱增，而且進一步在汽車以及二輪車之排氣裝置中亦多有使用。特別是基於替代先前之不鏽鋼素材、車輛輕量化之觀點，以二輪車為中心，JIS2種之工業用純鈦材已供使用。再者，近年以來，代替JIS2種之工業用純鈦材，耐熱性更高之耐熱鈦合金也已被使用。此外，為了除去廢氣之有害成分，搭載有高溫下使用之觸媒的消音器也已供使用。 Titanium materials are increasingly used in the field of aircraft based on their excellent specific strength and corrosion resistance, and are also used in automobile and two-wheel exhaust systems. In particular, based on the viewpoint of replacing the previous stainless steel materials and lightweight vehicles, JIS 2 industrial pure titanium materials have been used as the center of the two-wheeled vehicle. In addition, in recent years, in place of JIS 2 industrial pure titanium materials, heat-resistant titanium alloys having higher heat resistance have also been used. Further, in order to remove harmful components of the exhaust gas, a silencer equipped with a catalyst used at a high temperature is also used.
廢氣之溫度超過700℃，而且也有暫時到達800℃之情況。因此，使用於排氣裝置之素材乃被要求具有800℃左右之溫度下的強度、耐氧化性等，再者600~700℃下之蠕變速度的高溫耐熱性之指標也日益受到重 視。 The temperature of the exhaust gas exceeds 700 ° C, and there is also a case where it temporarily reaches 800 ° C. Therefore, the material used in the exhaust device is required to have a strength at a temperature of about 800 ° C, oxidation resistance, etc., and the high temperature heat resistance of the creep speed at 600 to 700 ° C is increasingly being heavily weighted. Vision.
另一方面，如此之耐熱鈦合金，為了提高其高溫強度，有添加Al、Cu及Nb此等可提升高溫強度及耐氧化性之元素的必要，其與工業用純鈦相比之下成本高昂。 On the other hand, in order to improve the high-temperature strength of such a heat-resistant titanium alloy, it is necessary to add elements such as Al, Cu, and Nb which can improve high-temperature strength and oxidation resistance, and it is costly compared with industrial pure titanium. .
日本特開2001-234266號公報(專利文獻1)中，曾揭示一種含Al：0.5~2.3%(本說明書中如無特別異議，有關化學成分之「%」均指「質量%」)之冷間加工性及高溫強度優異的鈦合金。 Japanese Laid-Open Patent Publication No. 2001-234266 (Patent Document 1) discloses a cold containing Al: 0.5 to 2.3% (in the present specification, if there is no special objection, "%" of the chemical component refers to "% by mass") A titanium alloy excellent in workability and high temperature strength.
日本特開2001-89821號公報(專利文獻2)中，曾揭示一種含Fe：大於1%且5%以下、O(氧)：0.05~0.75%，且進而含Si：0.01．e0.5[Fe]~5．e-0.5[Fe]之耐氧化性及耐蝕性優異的鈦合金([Fe]表示合金中之含有率(質量%)，e表示自然對數之常數)。 Japanese Laid-Open Patent Publication No. 2001-89821 (Patent Document 2) discloses that a Fe-containing content is more than 1% and 5% or less, O (oxygen): 0.05 to 0.75%, and further contains Si: 0.01. e 0.5[Fe] ~5. A titanium alloy excellent in oxidation resistance and corrosion resistance of e -0.5 [Fe] ([Fe] represents a content ratio (% by mass) in the alloy, and e represents a constant of a natural logarithm).
日本特開2005-290548號公報(專利文獻3)中，曾揭示一種含有Al：0.30~1.50%、Si：0.10~1.0%之冷間加工性優異的耐熱鈦合金板及其製造方法。 Japanese Laid-Open Patent Publication No. 2005-290548 (Patent Document 3) discloses a heat-resistant titanium alloy sheet containing Al: 0.30 to 1.50% and Si: 0.10 to 1.0%, which is excellent in cold workability, and a method for producing the same.
日本特開2009-68026號公報(專利文獻4)中，曾揭示一種含有Cu：0.5~1.8%、Si：0.1~0.6%、O：0.1%以下，且因應必要含有Nb：0.1~1.0%，且其餘部分由Ti及不可避免之雜質所構成之表面被覆有保護膜的鈦合金。 In Japanese Laid-Open Patent Publication No. 2009-68026 (Patent Document 4), it is disclosed that Cu: 0.5 to 1.8%, Si: 0.1 to 0.6%, O: 0.1% or less, and Nb: 0.1 to 1.0%, if necessary, The remaining portion is made of Ti and an unavoidable impurity, and the surface is covered with a protective film of a titanium alloy.
再者，日本特開2013-142183號公報(專利文獻5)中，曾揭示一種含有Si：0.1~0.6%、Fe：0.04~ 0.2%、O：0.02~0.15%，Fe與O之含量總量為0.1~0.3%，且其餘部分由Ti及不可避免之雜質元素所構成之700℃下的高溫強度及800℃下的耐氧化性優異之鈦合金。 Further, Japanese Laid-Open Patent Publication No. 2013-142183 (Patent Document 5) discloses that Si contains 0.1: 0.6% to 0.6% and Fe: 0.04%. 0.2%, O: 0.02~0.15%, the total content of Fe and O is 0.1-0.3%, and the rest is composed of Ti and unavoidable impurity elements, high temperature strength at 700 °C and oxidation resistance at 800 °C Excellent titanium alloy.
鈦材一般係利用以下所示之方法製造。首先，以克羅爾(Kroll)法將作為原料之氧化鈦氯化而形成四氯化鈦之後，以鎂或鈉還原之，藉而以塊狀製造海綿狀之金屬鈦(海綿鈦)。將此一海綿鈦壓製成形而形成為鈦消耗電極，將該鈦消耗電極作為電極進行真空電弧熔解而製造鈦錠。此時，因應必要添加合金元素而製造鈦合金錠。而後，將鈦合金錠分塊、鍛造、輥軋而形成鈦扁胚，然後進而將鈦扁胚熱軋、退火、酸洗、冷軋以及真空熱處理而製造鈦薄板。 Titanium is generally produced by the method shown below. First, titanium oxide as a raw material is chlorinated to form titanium tetrachloride by a Kroll method, and then reduced by magnesium or sodium, whereby a sponge-like metal titanium (sponge titanium) is produced in a bulk form. This sponge titanium was press-formed to form a titanium consumable electrode, and the titanium consumable electrode was subjected to vacuum arc melting as an electrode to produce a titanium ingot. At this time, a titanium alloy ingot is produced by adding an alloying element as necessary. Then, the titanium alloy ingot is divided, forged, and rolled to form a titanium flat embryo, and then the titanium flat blank is further subjected to hot rolling, annealing, pickling, cold rolling, and vacuum heat treatment to produce a titanium thin plate.
又，作為鈦薄板之製造方法，已有將鈦錠分塊、氫化粉碎、脫氫、粉末碎解以及分級而製造鈦粉末，並將鈦粉末作粉末輥軋、燒結及冷軋而予製造之方法為人所知。 Further, as a method for producing a titanium thin plate, a titanium ingot is divided into pieces, hydrocrushed, dehydrogenated, powder disintegrated, and classified to produce a titanium powder, and the titanium powder is produced by powder rolling, sintering, and cold rolling. The method is known.
日本特開2011-42828號公報(專利文獻6)中，曾揭示一種並非自鈦錠而是由海綿鈦直接製造鈦粉末，並自所獲得之鈦粉末製造鈦薄板之方法，為此，此鈦薄板之製造方法係將含鈦金屬粉、黏結劑、可塑劑、溶劑之黏性組成物成形為薄板狀之燒結前成形體予以燒結而製造燒結薄板，將該燒結薄板壓密而製造燒結壓密薄板，並將該燒結壓密薄板再燒結，其中使燒結薄板之破斷伸長量 為0.4%以上，使密度比為80%以上，並使燒結壓密板之密度比為90%以上。 Japanese Laid-Open Patent Publication No. 2011-42828 (Patent Document 6) discloses a method of producing a titanium thin plate from a titanium powder directly from a titanium ingot but directly from titanium sponge, and thereby producing titanium thin plate. The method for producing a thin plate is to form a sintered thin plate by forming a viscous composition containing a titanium metal powder, a binder, a plasticizer, and a solvent into a thin plate-like sintered body, and compacting the sintered sheet to produce a sintered compact. a thin plate, and the sintered compacted sheet is re-sintered, wherein the breaking elongation of the sintered thin plate is When the ratio is 0.4% or more, the density ratio is 80% or more, and the density ratio of the sintered compacted board is 90% or more.
日本特開2014-19945號公報(專利文獻7)中，曾揭示一種於以鈦合金邊角料或鈦合金錠為原料之鈦合金粉中，適量添加鐵粉、鉻粉或銅粉而形成為複合粉，將該複合粉作碳鋼包封擠壓，並將所獲得之圓棒之表面的包封溶解除去後，進而進行溶體化處理、或溶體化處理及時效處理，而以粉末法製造品質優異之鈦合金的方法。 Japanese Laid-Open Patent Publication No. 2014-19945 (Patent Document 7) discloses that a titanium alloy powder made of a titanium alloy scrap or a titanium alloy ingot is appropriately added with iron powder, chromium powder or copper powder to form a composite powder. The composite powder is encapsulated and extruded as carbon steel, and the encapsulation of the surface of the obtained round rod is dissolved and removed, and then subjected to a solution treatment or a solution treatment and a aging treatment, and is produced by a powder method. A method of high quality titanium alloy.
日本特開2001-131609號公報(專利文獻8)中，曾揭示一種將海綿鈦粉末填充於銅製包封後，於擠壓比1.5以上、擠壓溫度700℃以下實施溫間擠壓加工而成形，並實施將外側之銅除去的外周加工，而使成形體之粒界的全長之內20%以上為金屬接觸之鈦成形體製造方法。 In JP-A-2001-131609 (Patent Document 8), it has been disclosed that a titanium sponge powder is filled in a copper-clad form, and then formed by an inter-temperature extrusion process at an extrusion ratio of 1.5 or more and an extrusion temperature of 700 ° C or less. Further, the outer peripheral processing for removing the outer copper is performed, and 20% or more of the entire length of the grain boundary of the molded body is a metal contact titanium molded body.
於將熱軋素材予以熱軋時，當熱軋素材為純鈦或鈦合金般之因熱間延性不足以致熱間變形阻力值高之所謂難加工材的情形下，作為將其等輥軋成薄板之技術，疊板輥軋方法業已為人所知。疊板輥軋方法，係指將加工性不良之鈦合金等之芯材以加工性良好之價廉的碳鋼等之被覆材被覆而予熱軋之方法。 When the hot-rolled material is hot-rolled, when the hot-rolled material is a so-called difficult-to-machine material having a high heat-delay resistance such as pure titanium or a titanium alloy, the roll is rolled into The technology of thin sheets and the method of rolling sheets are well known. The laminating method refers to a method in which a core material such as a titanium alloy having poor workability is coated with a coating material such as carbon steel having good workability and is hot-rolled.
具體而言，例如係在芯材之表面塗佈剝離劑，至少將其上下二面以被覆材被覆，或是於上下面以外將其四周面以間隔材覆蓋，並將其四周熔接組合後再進行熱軋。疊板輥軋中，係將作為被輥軋材之芯材以被覆材被覆再進行熱軋。因此，芯材表面不會與冷態媒體(大氣或 輥)直接接觸，而可抑制芯材之溫度降低，故而即使是加工性不佳之芯材亦能夠製造薄板。 Specifically, for example, a release agent is applied to the surface of the core material, and at least the upper and lower surfaces thereof are coated with the covering material, or the peripheral surfaces thereof are covered with a spacer other than the upper and lower surfaces, and the surrounding portions are welded and combined. Hot rolling. In the lamination rolling, the core material of the rolled material is coated with a covering material and then hot rolled. Therefore, the core material surface does not interact with cold media (atmosphere or The roll is directly contacted, and the temperature of the core material can be suppressed from being lowered, so that even a core material having poor workability can be manufactured.
日本特開昭63-207401號公報(專利文獻9)中，曾揭示一種密閉被覆箱之組合方法；日本特開平09-136102號公報(專利文獻10)中，曾揭示一種在設為10-3Torr等級以上之真空度下將被覆材密封而製造密閉被覆箱之方法；再者，日本特開平11-057810號公報(專利文獻11)中，曾揭示一種以碳鋼(被覆材)被覆而在10-2Torr等級以下之真空下利用高能量密度熔接進行密封，而製造密閉被覆箱之方法。 Japanese Patent Laid-Open Publication No. 63-207401 (Patent Document 9), a composition has been disclosed a method of coating a sealed box; JP 09-136102 (Patent Document 10), has been disclosed to 10-3 A A method of producing a sealed coating box by sealing a covering material at a vacuum level of a Torr or higher, and a method of coating a carbon steel (coated material) in Japanese Patent Publication No. Hei 11-057810 (Patent Document 11) A method of manufacturing a sealed coated box by sealing with a high energy density welding under a vacuum of 10 -2 Torr or less.
另一方面，作為將耐蝕性高的素材廉價地製造之方法，已知的是將鈦材接合於作為母材之素材表面的方法。 On the other hand, as a method of manufacturing a material having high corrosion resistance at a low cost, a method of joining a titanium material to a surface of a material of a base material is known.
日本特開平08-141754號公報(專利文獻12)中，曾揭示一種作為母材使用鋼材且作為疊層材使用鈦或鈦合金，將母材與疊層材之接合面真空排氣之後予以熔接組合形成輥軋用組合扁胚，將此扁胚以熱軋接合之鈦包層鋼板的製造方法。 Japanese Patent Publication No. 08-141754 (Patent Document 12) discloses that a steel material is used as a base material, and titanium or a titanium alloy is used as a laminate, and the joint surface of the base material and the laminate is vacuum-exhausted and then welded. A method of producing a titanium-clad steel sheet in which a flat blank for rolling is combined and a flat-sheath is joined by hot rolling.
日本特開平11-170076號公報(專利文獻13)中，曾揭示一種於含有0.03質量%以上之碳的母材鋼材之表面上，介隔以由純鎳、純鐵及碳含量為0.01質量%以下之低碳鋼中之任一者所構成的厚度20μm以上之***材而積層配置鈦箔材之後，自其積層方向之任一方側照射雷射光束，而將鈦箔材之至少緣部附近遍及全周與母材鋼 材熔融接合，藉而製造鈦被覆鋼材之方法。 Japanese Laid-Open Patent Publication No. Hei 11-170076 (Patent Document 13) discloses that a surface of a base material steel material containing 0.03% by mass or more of carbon is separated by a content of pure nickel, pure iron, and carbon of 0.01% by mass. After the titanium foil is laminated and laminated with a thickness of 20 μm or more, which is formed of any of the following low carbon steels, the laser beam is irradiated from either side of the lamination direction, and at least the edge of the titanium foil is adjacent to the edge. Throughout the whole week with the base metal A method in which a material is melt-bonded to produce a titanium-coated steel material.
日本特開2015-045040號公報(專利文獻14)中，曾例示一種稠密狀鈦素材(鈦鑄塊)之形成方法，其係將成形為鑄塊狀之多孔質鈦原料(海綿鈦)的表面，於真空下使用電子射束熔解而製造表層部為稠密狀鈦的鈦鑄塊，並將其熱軋及冷軋，而以非常少之能量製造稠密狀鈦素材(鈦鑄塊)；此稠密狀鈦素材(鈦鑄塊)具備由多孔質鈦原料成形為鑄塊狀而成之多孔質部、及以稠密狀鈦構成且被覆多孔質部的所有表面之稠密被覆部。 In Japanese Laid-Open Patent Publication No. 2015-045040 (Patent Document 14), a method of forming a dense titanium material (titanium ingot) which is formed into a surface of a porous titanium material (sponge titanium) in the form of an ingot is exemplified. A titanium ingot having a surface layer of dense titanium is produced by electron beam melting under vacuum, and hot rolled and cold rolled, and a dense titanium material (titanium ingot) is produced with very little energy; The titanium material (titanium ingot) has a porous portion in which a porous titanium material is formed into an ingot shape, and a dense coating portion which is made of dense titanium and covers all surfaces of the porous portion.
日本特開昭62-270277號公報(專利文獻15)中，曾記載利用熔射進行汽車用引擎構件之表面效果處理。 In JP-A-62-270277 (Patent Document 15), the surface effect treatment of an automobile engine member by spraying is described.
[專利文獻1]日本特開2001-234266號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-234266
[專利文獻2]日本特開2001-89821號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-89821
[專利文獻3]日本特開2005-290548號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-290548
[專利文獻4]日本特開2009-68026號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-68026
[專利文獻5]日本特開2013-142183號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2013-142183
[專利文獻6]日本特開2011-42828號公報 [Patent Document 6] Japanese Laid-Open Patent Publication No. 2011-42828
[專利文獻7]日本特開2014-19945號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2014-19945
[專利文獻8]日本特開2001-131609號公報 [Patent Document 8] Japanese Laid-Open Patent Publication No. 2001-131609
[專利文獻9]日本特開昭63-207401號公報 [Patent Document 9] JP-A-63-207401
[專利文獻10]日本特開平09-136102號公報 [Patent Document 10] Japanese Patent Laid-Open No. 09-136102
[專利文獻11]日本特開平11-057810號公報 [Patent Document 11] Japanese Patent Laid-Open No. Hei 11-057810
[專利文獻12]日本特開平08-141754號公報 [Patent Document 12] Japanese Laid-Open Patent Publication No. 08-141754
[專利文獻13]日本特開平11-170076號公報 [Patent Document 13] Japanese Patent Laid-Open No. Hei 11-170076
[專利文獻14]日本特開2015-045040號公報 [Patent Document 14] Japanese Patent Laid-Open Publication No. 2015-045040
[專利文獻15]日本特開昭62-270277號公報 [Patent Document 15] Japanese Laid-Open Patent Publication No. 62-270277
專利文獻1所揭示之鈦合金，由於添加有Al，因此對於成形加工性，特別是對在厚度減少之方向由加工所引起之拉伸成形性帶來不良影響。 In the titanium alloy disclosed in Patent Document 1, since Al is added, the formability is particularly adversely affected by the draw formability caused by the processing in the direction in which the thickness is reduced.
專利文獻2所揭示之鈦合金，Fe與O合計含量多，因此室溫下之強度超過800N/mm2而過強，且其伸長量也在20%以下而缺乏成形性。 The titanium alloy disclosed in Patent Document 2 has a large content of Fe and O. Therefore, the strength at room temperature exceeds 800 N/mm 2 and is too strong, and the elongation thereof is also 20% or less, and the formability is lacking.
專利文獻3所揭示之鈦合金，與上述相同添加有Al，因此冷間加工性，特別是對在厚度減少之方向由加工所引起之拉伸成形性有帶來不良影響之虞。 In the titanium alloy disclosed in Patent Document 3, since Al is added in the same manner as described above, the cold workability, particularly the stretch formability due to processing in the direction in which the thickness is reduced, is adversely affected.
專利文獻4所揭示之鈦合金，雖然具有充分之加工性及耐氧化特性，然因多量含有高價之Nb，合金成本提高。 Although the titanium alloy disclosed in Patent Document 4 has sufficient workability and oxidation resistance, the alloy cost is increased because a large amount of Nb is contained in a large amount.
再者，專利文獻5所揭示之鈦合金所亦具有充分之高溫氧化特性，然因板全面合金化，合金成本提高。 Further, the titanium alloy disclosed in Patent Document 5 also has sufficient high-temperature oxidation characteristics, and the alloy cost is increased due to the overall alloying of the sheet.
先前，於經由熱間加工製造鈦材時，係將海綿鈦壓製成形形成為鈦消耗電極，並將該鈦消耗電極作為電極進行真空電弧熔解而製造鈦錠，然後進而將該鈦錠分塊、鍛造、輥軋而形成鈦扁胚，再將該鈦扁胚熱軋、退火、酸洗、冷軋而完成製造。 In the prior art, when a titanium material is produced by hot working, a sponge titanium is press-formed into a titanium consumable electrode, and the titanium consumable electrode is used as an electrode to perform vacuum arc melting to produce a titanium ingot, and then the titanium ingot is further divided, The titanium flat embryo is formed by forging and rolling, and the titanium flat blank is further subjected to hot rolling, annealing, pickling, and cold rolling to complete the production.
此一情形下，一定要追加將鈦熔解而製造鈦錠之步驟。按將鈦粉末予以粉末輥軋、燒結、及冷軋而進行製造之方法雖也屬既知，但自鈦錠製造鈦粉末之方法，畢竟還是要追加將鈦熔解之步驟。 In this case, it is necessary to add a step of melting titanium to produce a titanium ingot. Although a method of producing titanium powder by powder rolling, sintering, and cold rolling is also known, a method of producing titanium powder from a titanium ingot is required to add a step of melting titanium.
於自鈦粉末製造鈦材之方法中，即使未經熔解步驟，由於仍是以高價之鈦粉末作為原料使用，因此所獲得之鈦材變得非常高價。專利文獻9~專利文獻10所揭示之方法亦相同。 In the method for producing a titanium material from titanium powder, even if it is not used as a raw material without using a high-priced titanium powder, the obtained titanium material becomes very expensive. The methods disclosed in Patent Documents 9 to 10 are also the same.
疊板輥軋中，由被覆材被覆之芯材無論如何都是扁胚或錠，雖然經由熔解步驟，然其係以高價之鈦粉末為原料，無法降低製造成本。 In the lamination rolling, the core material coated with the covering material is in any case a flat embryo or an ingot, and although it is made of a high-priced titanium powder as a raw material through a melting step, the manufacturing cost cannot be reduced.
專利文獻14中，可以非常少之能量製造稠密狀鈦素材，然其係規定將成形為鑄塊狀之海綿鈦的表面熔解，且稠密狀鈦表層部及內部之成分為同種之純鈦或鈦合金，例如，藉由只於表層部將鈦合金層均一且遍及廣範圍地形成，無法謀求製造成本之降低。 In Patent Document 14, a dense titanium material can be produced with very little energy. However, it is required to melt the surface of the sponge titanium formed into a cast shape, and the dense titanium surface layer and the inner composition are the same kind of pure titanium or titanium. In the alloy, for example, the titanium alloy layer is formed uniformly and over a wide range only in the surface layer portion, and the manufacturing cost cannot be reduced.
另一方面，可製造價廉之耐蝕素材的於母材之表面接合以鈦或鈦合金而成之素材，作為母材大多是選擇鋼。因此，表面之鈦層若是失去則有損耐蝕性。假設母 材亦採用鈦材，只要是使用經由一般之製造步驟所製造之鈦材，無法期待根本性之成本改善。因此，本發明人等乃考量到於工業用純鈦或鈦合金所構成之扁胚的表層設置含有特定之合金元素的合金層，而獲得價廉且特定性能優異之鈦材。 On the other hand, a material made of titanium or a titanium alloy is bonded to the surface of the base material at an inexpensive corrosion-resistant material, and most of the base material is steel. Therefore, if the titanium layer on the surface is lost, the corrosion resistance is impaired. Assume mother Titanium is also used as the material, and as long as the titanium material produced by the general manufacturing steps is used, a fundamental cost improvement cannot be expected. Therefore, the present inventors have considered that an alloy layer containing a specific alloying element is provided on the surface layer of a flat embryo composed of industrial pure titanium or a titanium alloy, and a titanium material excellent in cost and excellent in specific properties is obtained.
如專利文獻15般，熔射係將金屬、陶瓷等熔融，並噴至鈦材表面而形成皮膜之方法。根據此一方法形成皮膜時，皮膜中之氣孔的形成無可避免。通常，於熔射時為了避免皮膜之氧化，係一面以惰性氣體屏蔽一面進行熔射。此等惰性氣體會捲入皮膜之氣孔內。內含如此之惰性氣體的氣孔，以熱間加工等不會壓著。又，鈦之製造中，一般係實施真空熱處理，然於此處理時，氣孔內之惰性氣體會膨脹以致皮膜有剝離之虞。根據本發明人等之經驗，熔射所生之氣孔的存在率(空隙率)為數vol.%以上，依熔射條件還有大於10vol.%之情形。如此，皮膜內之空隙率高的鈦材，於製造步驟中會有剝離之危險性，而且還會有加工時之破裂等缺損發生之虞。 As in Patent Document 15, a melting method is a method in which a metal, a ceramic, or the like is melted and sprayed onto a surface of a titanium material to form a film. When the film is formed according to this method, the formation of pores in the film is inevitable. Usually, in order to avoid oxidation of the film during the spraying, the film is sprayed while being shielded with an inert gas. These inert gases are drawn into the pores of the membrane. The pores containing such an inert gas are not pressed by heat processing or the like. Further, in the production of titanium, vacuum heat treatment is generally carried out. However, during the treatment, the inert gas in the pores expands to cause peeling of the film. According to the experience of the inventors of the present invention, the existence ratio (void ratio) of the pores generated by the spray is several vol.% or more, and the molten condition is more than 10 vol.%. As described above, the titanium material having a high void ratio in the film may be peeled off during the production step, and there may be defects such as breakage during processing.
作為皮膜之形成方法，有一種為冷噴法。根據此一方法，於表面形成皮膜之情形亦然，使用惰性之高壓氣體。根據此一方法，依其條件雖可將空隙率設為小於1vol.%，但將氣孔之發生完全防止極為困難。而且，與熔射之情況相同，氣孔中內含惰性氣體，因此即使借助後續之加工也不會消滅。又，於真空中施以熱處理之情況下，氣孔內之惰性氣體會膨脹，以致皮膜有破裂之顧慮。 As a method of forming the film, there is a cold spray method. According to this method, it is also the case that a film is formed on the surface, and an inert high pressure gas is used. According to this method, the void ratio can be made less than 1 vol.% depending on the conditions, but it is extremely difficult to completely prevent the occurrence of pores. Moreover, as in the case of the spray, the pores contain an inert gas, so that they are not destroyed even by subsequent processing. Further, in the case where heat treatment is applied in a vacuum, the inert gas in the pores may swell, so that the film may be broken.
為了抑制熱軋時之表面瑕疵，作為使用電子射束熔融扁胚之表層並予再凝固之處理，有一種是熔融再凝固處理。通常，熔融再凝固之表層，係由熱軋後之酸洗步驟除去。因此，先前之熔融再凝固處理中，針對表層部之合金成分的偏析完全未考慮。 In order to suppress the surface flaw during hot rolling, as a treatment for melting the surface layer of the flat embryo with an electron beam and re-solidifying, there is a melt re-solidification treatment. Usually, the surface layer which is melted and resolidified is removed by a pickling step after hot rolling. Therefore, in the previous melt resolidification treatment, segregation of the alloy component of the surface layer portion was not considered at all.
是以，本發明人等乃思及於工業用純鈦或鈦合金所構成之扁胚的表面上，貼附含有特定之合金元素的鈦板，並將所得物用作為熱軋用素材，而據以獲得價廉且特定性能優異之鈦材。 The present inventors have attached a titanium plate containing a specific alloying element to the surface of a flat embryo made of pure titanium or a titanium alloy for industrial use, and used the resultant as a material for hot rolling. According to the titanium material which is inexpensive and has excellent performance.
本發明之目的在於藉由降低為了提升耐氧化性而添加之合金元素的含量(為了表現目標特性之特定的合金元素之使用量)，且抑制鈦材之製造成本，而價廉地獲得具備耐氧化性的鈦複合材以及熱軋用鈦材。 An object of the present invention is to obtain a resistance at a low cost by reducing the content of an alloying element added to enhance oxidation resistance (the amount of a specific alloying element used to express a target characteristic) and suppressing the manufacturing cost of the titanium material. Oxidized titanium composite and titanium for hot rolling.
本發明係為解決上述課題而開發完成，係以下述之鈦複合材以及熱軋用鈦材為其要旨。 The present invention has been developed to solve the above problems, and is based on the following titanium composite materials and titanium materials for hot rolling.
(1)一種鈦複合材，具備：內層，其含有工業用純鈦或鈦合金；表層，其形成於前述內層之至少一方的輥軋面上，具有與前述內層不同之化學組成；及中間層，其形成於前述內層與前述表層之間，具有與前述內層不同之化學組成；而且前述表層，其厚度為2μm以上，且占總厚度之比率 每個單面之層為40%以下；前述表層部之化學組成，以質量%計為：選自Si：0.1~0.6%、Nb：0.1~2.0%、Ta：0.3~1.0%及Al：0.3~1.5%之一種以上、Sn：0~1.5%、Cu：0~1.5%、Fe：0~0.5%、以及其餘部分：鈦及雜質；前述中間層之厚度為0.5μm以上。 (1) A titanium composite material comprising: an inner layer containing industrial pure titanium or a titanium alloy; and a surface layer formed on at least one of the rolled surfaces of the inner layer, having a chemical composition different from the inner layer; And an intermediate layer formed between the inner layer and the surface layer, having a chemical composition different from the inner layer; and the surface layer has a thickness of 2 μm or more and a ratio of total thickness The layer of each single side is 40% or less; the chemical composition of the surface layer portion is, in mass%, selected from the group consisting of Si: 0.1 to 0.6%, Nb: 0.1 to 2.0%, Ta: 0.3 to 1.0%, and Al: 0.3. ~1.5% or more, Sn: 0 to 1.5%, Cu: 0 to 1.5%, Fe: 0 to 0.5%, and the balance: titanium and impurities; the thickness of the intermediate layer is 0.5 μm or more.
(2)如上述(1)之鈦複合材，其中前述內層的輥軋面以外之面上，形成有其他之表層；前述其他之表層具有與前述表層相同之化學組成。 (2) The titanium composite material according to (1) above, wherein the surface layer other than the rolled surface of the inner layer is formed with another surface layer; and the other surface layer has the same chemical composition as the surface layer.
(3)一種熱軋用鈦材，具備：母材，其含有工業用純鈦或鈦合金；表層材，其接合於前述母材之至少一方的輥軋面；及熔接部，其接合前述母材與前述表層材之周圍；且前述表層材具有與前述母材不同之化學組成，且以質量%計為：選自Si：0.1~0.6%、Nb：0.1~2.0%、Ta：0.3~1.0%及Al：0.3~1.5%之一種以上、Sn：0~1.5%、Cu：0~1.5%、Fe：0~0.5%、以及其餘部分：鈦及雜質； 前述熔接部將前述母材與前述表層材之界面自外氣遮斷。 (3) A titanium material for hot rolling, comprising: a base material containing industrial pure titanium or a titanium alloy; a surface layer joined to at least one of the rolled surfaces of the base material; and a welded portion joining the mother a material and a periphery of the surface layer; and the surface layer has a chemical composition different from the base material, and is selected from mass: from: Si: 0.1 to 0.6%, Nb: 0.1 to 2.0%, and Ta: 0.3 to 1.0. % and Al: one or more of 0.3 to 1.5%, Sn: 0 to 1.5%, Cu: 0 to 1.5%, Fe: 0 to 0.5%, and the rest: titanium and impurities; The welded portion blocks the interface between the base material and the surface layer from the outside air.
(4)如上述(3)之熱軋用鈦材，其中前述母材的輥軋面以外之面上，接合有其他之表層材；前述其他之表層材具有與前述表層材相同之化學組成。 (4) The titanium material for hot rolling according to (3) above, wherein the surface layer other than the rolled surface of the base material is joined to another surface layer material; and the other surface layer material has the same chemical composition as the surface layer material.
(5)如上述(3)或(4)之熱軋用鈦材，其中前述母材包含直接鑄造扁胚。 (5) The titanium material for hot rolling according to (3) or (4) above, wherein the base material comprises a directly cast flat embryo.
(6)如上述(5)之熱軋用鈦材，其中前述直接鑄造扁胚，其表面之至少一部分形成有熔融再凝固層。 (6) The titanium material for hot rolling according to (5) above, wherein the directly cast flat embryo has at least a part of a surface thereof formed with a molten resolidified layer.
(7)如上述(6)之熱軋用鈦材，其中前述熔融再凝固層之化學組成與前述直接鑄造扁胚的板厚中心部之化學組成不同。 (7) The titanium material for hot rolling according to (6) above, wherein the chemical composition of the molten resolidified layer is different from the chemical composition of the center portion of the thickness of the directly cast flat embryo.
本發明相關之鈦複合材，具備：含有工業用純鈦或鈦合金之內層、以及具有與內層不同的化學組成之表層，因此與整體為相同鈦合金所構成之鈦材比較，具有同等之耐氧化性，然而能夠價廉地製造。 The titanium composite material according to the present invention has an inner layer containing industrial pure titanium or a titanium alloy and a surface layer having a chemical composition different from that of the inner layer, and therefore has the same degree as a titanium material composed of the same titanium alloy as a whole. It is resistant to oxidation, but can be manufactured inexpensively.
1、2‧‧‧鈦複合材 1, 2‧‧‧ Titanium composite
3、4‧‧‧表層 3, 4‧‧‧ surface
5‧‧‧內層 5‧‧‧ inner layer
6‧‧‧母材(扁胚) 6‧‧‧ parent material (flat embryo)
7、8‧‧‧表層材(鈦板) 7,8‧‧‧Materials (titanium plate)
9‧‧‧熔接部 9‧‧‧welding department
第1圖為表示本發明相關之鈦複合材的構成之一例的說明圖。 Fig. 1 is an explanatory view showing an example of the configuration of a titanium composite material according to the present invention.
第2圖為表示本發明相關之鈦複合材的構成之一例的說明圖。 Fig. 2 is an explanatory view showing an example of the configuration of a titanium composite material according to the present invention.
第3圖為示意性表示藉由將鈦矩形鑄片與鈦板在真空中熔接，而予貼合的說明圖。 Fig. 3 is an explanatory view schematically showing a state in which a titanium rectangular cast piece and a titanium plate are welded in a vacuum.
第4圖為示意性表示藉由不僅於鈦矩形鑄片之表面而且又於其側面上將鈦板熔接，而予貼合的說明圖。 Fig. 4 is an explanatory view schematically showing a state in which a titanium plate is welded not only to the surface of the titanium rectangular cast piece but also to the side surface thereof.
第5圖為表示熔融再凝固之方法的說明圖。 Fig. 5 is an explanatory view showing a method of melting and resolidifying.
第6圖為表示熔融再凝固之方法的說明圖。 Fig. 6 is an explanatory view showing a method of melting and resolidifying.
第7圖為表示熔融再凝固之方法的說明圖。 Fig. 7 is an explanatory view showing a method of melting and resolidifying.
本發明人等，為了解決上述課題，藉由僅將最終製品之鈦板的表層合金化，而減少表現耐氧化性之特定之合金元素的使用量，且為了抑制鈦材之製造成本，而展開銳意研討之結果，終而發現一種將含有工業用純鈦或鈦合金之母材與具有與母材不同的化學組成之表層材，以將其等之界面自外氣遮斷之方式，將該母材及表層材之周圍熔接而成之熱軋用鈦材。將該熱軋用鈦材熱間加工所得之鈦複合材，可成為價廉地具有優異之耐氧化性的鈦材。 In order to solve the above problems, the inventors of the present invention have reduced the use amount of a specific alloying element which exhibits oxidation resistance by alloying only the surface layer of the titanium plate of the final product, and have been developed to suppress the production cost of the titanium material. As a result of intensive research, it was discovered that a base material containing industrial pure titanium or titanium alloy and a surface material having a chemical composition different from that of the base material were used to block the interface of the material from the outside air. A titanium material for hot rolling in which the base material and the surface layer are welded together. The titanium composite obtained by hot-working the titanium material for hot rolling can be a titanium material which is excellent in oxidation resistance and which is excellent in oxidation resistance.
本發明係基於上述知識及見解而完成者。以下，茲將本發明相關之鈦複合材以及其熱軋用之鈦材，一 面參照圖面一面說明。又，以下之說明中，有關各元素之含量的「%」，如未特別異議，均是指「質量%」。 The present invention has been completed based on the above knowledge and insights. Hereinafter, the titanium composite material according to the present invention and the titanium material for hot rolling thereof are used. The surface is described with reference to the drawing. In addition, in the following description, "%" of the content of each element means "mass%" unless it is especially dissatisfied.
如第1、2圖所示，鈦複合材1、2具備：含有工業用純鈦或鈦合金之內層5、形成於內層5之至少一方的輥軋面且具有與內層5不同的化學組成之表層3、4、以及形成於內層5與表層3、4之間且具有與內層5不同的化學組成之中間層(圖示省略)。又，於第1、2圖所示之例子中，所表示的是於內層5之一方或兩方的輥軋面形成表層之例子，也可在內層5的輥軋面以外之面(第1、2圖所示之例子中為側面)上設置其他之表層(圖示省略)。以下，針對表層、內層、中間層依序說明。 As shown in the first and second figures, the titanium composite materials 1 and 2 include an inner layer 5 containing industrial pure titanium or a titanium alloy, and a rolled surface formed on at least one of the inner layers 5 and having a different surface from the inner layer 5. The chemical composition of the surface layers 3, 4, and an intermediate layer (not shown) formed between the inner layer 5 and the surface layers 3, 4 and having a chemical composition different from that of the inner layer 5. Further, in the examples shown in Figs. 1 and 2, an example in which the surface layer is formed on one or both of the rolling faces of the inner layer 5 may be used, and the surface of the inner layer 5 may be other than the rolling surface ( In the examples shown in Figs. 1 and 2, other surface layers are provided on the side surface (not shown). Hereinafter, the surface layer, the inner layer, and the middle layer will be described in order.
表層之厚度若是過薄，則無法充分獲得所期望之特性。另一方面，若是過厚則鈦複合材整體中鈦合金所占的比率會增大，成本優勢將會減小。因此，其厚度設為2μm以上，且占總厚度之比率設為就每個單面之層為40%以下。 If the thickness of the surface layer is too thin, the desired characteristics cannot be sufficiently obtained. On the other hand, if it is too thick, the ratio of the titanium alloy in the entire titanium composite material will increase, and the cost advantage will be reduced. Therefore, the thickness is set to 2 μm or more, and the ratio of the total thickness is set to 40% or less for each single-sided layer.
表層之中，與外部環境相接之表層的厚度若是過薄，則無法充分獲得耐氧化性。表層之厚度雖依製造所用之素 材的厚度、或其後之加工率而變化，但若是2μm以上則可發揮充分效果。因此，表層之厚度宜為5μm以上，更令人滿意的是10μm以上。 In the surface layer, if the thickness of the surface layer in contact with the external environment is too thin, oxidation resistance cannot be sufficiently obtained. The thickness of the surface layer is based on the factors used in manufacturing. The thickness of the material or the subsequent processing rate varies, but if it is 2 μm or more, a sufficient effect can be exhibited. Therefore, the thickness of the surface layer is preferably 5 μm or more, and more desirably 10 μm or more.
另一方面，表層厚的情形下，耐氧化性雖無問題，但鈦複合材整體中鈦合金所占的比率增大，成本優勢減小。因此，相對鈦複合材之總厚度之表層的厚度之比率，令人滿意的是每個單面之層為40%以下，更令人滿意的是30%以下。 On the other hand, in the case where the surface layer is thick, although the oxidation resistance is not problematic, the ratio of the titanium alloy in the entire titanium composite material is increased, and the cost advantage is reduced. Therefore, the ratio of the thickness of the surface layer to the total thickness of the titanium composite material is satisfactorily 40% or less per one-sided layer, and more desirably 30% or less.
本發明相關之鈦複合材1中，為了提升表層之至少一者(至少與外部環境相接之表層)的耐蝕性，可含有以下所揭示之各種合金元素。 In the titanium composite material 1 according to the present invention, in order to improve the corrosion resistance of at least one of the surface layers (at least the surface layer in contact with the external environment), various alloying elements disclosed below may be contained.
Si具有提升600~800℃之高溫下的耐氧化性之作用。Si含量若小於0.1%，則對於耐氧化性之提升限度小。另一方面，Si含量若是大於0.6%，則對於耐氧化性之影響飽和，且不只室溫而且高溫下之加工性顯著降低。因此，於含有Si之情形下，其含量設為0.1~0.6%。Si含量宜為0.15%以上，更好的是0.20%以上。而且，宜為0.55%以下，更好的是0.50%以下。 Si has the effect of increasing the oxidation resistance at a high temperature of 600 to 800 °C. When the Si content is less than 0.1%, the increase in oxidation resistance is small. On the other hand, when the Si content is more than 0.6%, the effect on oxidation resistance is saturated, and the workability at room temperature and high temperature is remarkably lowered. Therefore, in the case of containing Si, the content is set to 0.1 to 0.6%. The Si content is preferably 0.15% or more, more preferably 0.20% or more. Further, it is preferably 0.55% or less, more preferably 0.50% or less.
Nb也具有提升高溫下之耐氧化性的作用。為了提升耐氧化性，Nb含量設為0.1%以上。另一方面，Nb含量即使超過2.0%效果也會飽和，而且由於Nb為高價之添加元素，與合金成本之增加息息相關。因此，於含有Nb之情形下，其含量設為0.1~2.0%。Nb含量宜為0.3%以上，更好的是0.5%以上。而且，宜為1.5%以下，更好的是1.0%以下。 Nb also has the effect of increasing the oxidation resistance at high temperatures. In order to improve oxidation resistance, the Nb content is set to 0.1% or more. On the other hand, even if the Nb content exceeds 2.0%, the effect is saturated, and since Nb is a high-priced additive element, it is closely related to the increase in the cost of the alloy. Therefore, in the case of containing Nb, the content thereof is set to 0.1 to 2.0%. The Nb content is preferably 0.3% or more, more preferably 0.5% or more. Further, it is preferably 1.5% or less, more preferably 1.0% or less.
Ta也具有提升高溫下之耐氧化性的作用。為了提升耐氧化性，Ta含量設為0.3%以上。另一方面，Ta含量若以超過1.0%含有，由於Ta為高價之添加元素，與合金成本之增加息息相關，而且根據熱處理溫度，β相之生成也令人懸念。因此，於含有Ta之情形下，其含量設為0.3~1.0%。Ta含量宜為0.4%以上，更好的是0.5%以上。而且，宜為0.9%以下，更好的是0.8%以下。 Ta also has the effect of increasing the oxidation resistance at high temperatures. In order to improve oxidation resistance, the Ta content is set to 0.3% or more. On the other hand, if the Ta content is more than 1.0%, since Ta is a high-priced additive element, it is closely related to the increase in the cost of the alloy, and the formation of the β phase is also suspense depending on the heat treatment temperature. Therefore, in the case where Ta is contained, the content thereof is set to 0.3 to 1.0%. The Ta content is preferably 0.4% or more, more preferably 0.5% or more. Further, it is preferably 0.9% or less, more preferably 0.8% or less.
Al也是提升高溫下之耐氧化性的元素。另一方面，Al若是多量含有，則室溫下之延性將顯著降低。Al含量若為0.3%以上，則可充分表現耐氧化特性。又，Al含量若是1.5%以下，則可充分保證冷間加工。因此，在含有Al之情形下，其含量設為0.3~1.5%。Al含量宜為0.4%以上，更好的是0.5%以上。而且，宜為1.2%以下。 Al is also an element that enhances the oxidation resistance at high temperatures. On the other hand, if Al is contained in a large amount, the ductility at room temperature will be remarkably lowered. When the Al content is 0.3% or more, the oxidation resistance can be sufficiently exhibited. Further, when the Al content is 1.5% or less, the cold room processing can be sufficiently ensured. Therefore, in the case where Al is contained, the content thereof is set to 0.3 to 1.5%. The Al content is preferably 0.4% or more, more preferably 0.5% or more. Moreover, it is preferably 1.2% or less.
又，Si、Nb、Ta及Al，若是各自單獨含有雖可使耐氧化性提升，但藉由複合含有，則可使耐高溫氧化性進一步提升。 Further, Si, Nb, Ta, and Al, if they are contained separately, can improve oxidation resistance, but by containing them in combination, the high-temperature oxidation resistance can be further improved.
除了上述之元素以外，可含有選自Sn、Cu及Fe之一種以上。 In addition to the above elements, one or more selected from the group consisting of Sn, Cu, and Fe may be contained.
Sn為α相安定化元素，且與Cu相同，乃可提高高溫強度之元素。然而，Sn含量若大於1.5%，則會抑制雙晶變形，而降低室溫下之加工性。因此，於含有Sn之情形下，其含量設為1.5%以下。Sn含量宜為1.3%以下，更好的是1.2%以下。在企圖獲得上述效果之情形下，Sn含量宜為0.2%以上，更好的是0.5%以上。 Sn is an α-phase-stabilizing element and, like Cu, is an element which can improve high-temperature strength. However, if the Sn content is more than 1.5%, the twin crystal deformation is suppressed, and the workability at room temperature is lowered. Therefore, in the case where Sn is contained, the content thereof is set to 1.5% or less. The Sn content is preferably 1.3% or less, more preferably 1.2% or less. In the case where the above effects are attempted, the Sn content is preferably 0.2% or more, more preferably 0.5% or more.
Cu為提高高溫強度之元素。而且，以一定程度固溶於α相，因此即使於高溫下使用時也不會生成β相。然而，Cu含量若大於1.5%，則根據溫度而生成β相。因此，於含有Cu之情形下，其含量設為1.5%以下。Cu含量宜為1.4%以下，更好的是1.2%以下。在企圖獲得上述效果之情形下，Cu含量宜為0.2%以上，更好的是0.4%以上。 Cu is an element that increases the strength of high temperature. Further, since it is dissolved in the α phase to a certain extent, the β phase is not formed even when used at a high temperature. However, if the Cu content is more than 1.5%, the β phase is formed depending on the temperature. Therefore, in the case where Cu is contained, the content thereof is set to 1.5% or less. The Cu content is preferably 1.4% or less, more preferably 1.2% or less. In the case of attempting to obtain the above effects, the Cu content is preferably 0.2% or more, more preferably 0.4% or more.
Fe為β相安定化元素，若為少量則β相之生成少，對於耐氧化性並無大的影響。然而，Fe含量若是超過0.5%則β相之生成量增多，而使耐氧化性劣化。因此，於含有Fe之情形下，其含量設為0.5%以下。Fe含量宜為0.4%以下，更好的是0.3%以下。 Fe is a β phase stabilizer element, and if it is a small amount, the generation of the β phase is small, and it does not have a large influence on oxidation resistance. However, when the Fe content is more than 0.5%, the amount of formation of the β phase increases, and the oxidation resistance is deteriorated. Therefore, in the case where Fe is contained, the content thereof is set to 0.5% or less. The Fe content is preferably 0.4% or less, more preferably 0.3% or less.
Sn、Cu及Fe之合計含量若是超過2.5%，會造成室溫下之加工性降低，變得根據溫度而β相生成。因此，於含有選自Sn、Cu及Fe之一種以上的情形下，其合計含量宜設為2.5%以下。 When the total content of Sn, Cu, and Fe exceeds 2.5%, the workability at room temperature is lowered, and the β phase is formed depending on the temperature. Therefore, in the case where one or more selected from the group consisting of Sn, Cu, and Fe are contained, the total content thereof is preferably 2.5% or less.
上述以外之其餘部分為雜質。作為雜質，可以不妨害目標特性之範圍含有，其他之雜質主要包括作為自邊角料混入之雜質元素的Cr、V、Cr、Mn及Mo等，與一般之雜質元素C、N、O及H合計，總量若是5%以下可容許。 The remainder other than the above is an impurity. As an impurity, it may be contained in a range that does not impair the target characteristics, and other impurities mainly include Cr, V, Cr, Mn, and Mo which are impurity elements mixed from the scrap, and are combined with general impurity elements C, N, O, and H, If the total amount is 5% or less, it is acceptable.
內層5含有工業用純鈦或鈦合金。例如，內層5若使用工業用純鈦，則與整體含有相同之鈦合金的鈦材比較，室溫下之加工性優異。 The inner layer 5 contains industrial pure titanium or a titanium alloy. For example, when industrial pure titanium is used for the inner layer 5, it is excellent in workability at room temperature as compared with a titanium material containing the same titanium alloy as a whole.
又，此處所稱之工業用純鈦，包括JIS規格之1種~4種、以及與其對應之ASTM規格之Grade1~4、DIN規格之3.7025、3.7035、3.7055所規定之工業用純鈦。亦即，本發明中作為對象之工業用純鈦，例如含有：C：0.1%以下、H：0.015%以下、O：0.4%以下、N： 0.07%以下、Fe：0.5%以下、其餘部分之Ti。 Further, the industrial pure titanium referred to herein includes one to four kinds of JIS standards, and the industrial pure titanium specified in Grades 1 to 4 of ASTM specifications and 3.7025, 3.7035, and 3.7055 of DIN specifications. In other words, the pure titanium for industrial use in the present invention contains, for example, C: 0.1% or less, H: 0.015% or less, and O: 0.4% or less, and N: 0.07% or less, Fe: 0.5% or less, and the rest of Ti.
又，除了特定之性能以外，於供使用於亦被要求強度之用途時，內層5可使用鈦合金。藉由提高表層之B含量且將內層5以鈦合金構成，可大幅降低合金成本且可獲得高強度。 Further, in addition to the specific properties, the titanium alloy may be used for the inner layer 5 when it is used for applications where strength is also required. By increasing the B content of the surface layer and the inner layer 5 being made of a titanium alloy, the alloy cost can be greatly reduced and high strength can be obtained.
形成內層5之鈦合金，因應必要之用途，可使用α型鈦合金、α+β型鈦合金、β型鈦合金之任何一種。 The titanium alloy forming the inner layer 5 may be any one of an α type titanium alloy, an α + β type titanium alloy, and a β type titanium alloy, depending on the intended use.
此處，作為α型鈦合金，可使用例如高耐蝕性合金(ASTM Grade 7,11,16,26,13,30,33或是與其等對應之JIS種或進而少量含有各種元素之鈦材)、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等。 Here, as the α-type titanium alloy, for example, a highly corrosion-resistant alloy (ASTM Grade 7, 11, 16, 26, 13, 30, 33 or a JIS species corresponding thereto or a small amount of a titanium material containing various elements) may be used. , 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, and the like.
作為α+β型鈦合金，可使用例如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等。 As the α + β type titanium alloy, for example, Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-7V, Ti-3Al-5V, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti can be used. -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.
再者，作為β型鈦合金，可使用例如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等。 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, or the like can be used. Ti-15V-3Al-3Cr-3Sn, Ti-6.8Mo- 4.5Fe-1.5Al, Ti-20V-4Al-1Sn, Ti-22V-4Al, and the like.
惟，若是內層5之0.2%耐力大於1000MPa，則加工性惡化，例如在彎曲加工時有發生破裂之虞。因此，令人滿意的是，使用於內層5之鈦以及鈦合金，其0.2%耐力在1000MPa以下。 However, if the 0.2% proof endurance of the inner layer 5 is more than 1000 MPa, the workability is deteriorated, for example, cracking occurs during bending. Therefore, it is desirable that the titanium used for the inner layer 5 and the titanium alloy have a 0.2% proof force of 1000 MPa or less.
本發明之鈦複合材，在前述內層與前述表層之間具備中間層。亦即，後述之熱軋用鈦材，雖係於母材貼附表層材並將周圍熔接而成者，但在其後之熱軋加熱時以及冷軋後之熱處理步驟中，母材與表層材之界面處會產生擴散，而在最終加工成鈦複合材時，上述來自母材之內層與來自上述表層材之表層之間乃形成中間層。此一中間層，具有與母材之化學組成不同之化學組成。此一中間層與上述內層及上述表層金屬鍵結而強固地接合。又，由於在中間層產生連續之元素梯度，因此可緩和上述內層與上述表層之強度差，而抑制加工時之破裂。 The titanium composite of the present invention has an intermediate layer between the inner layer and the surface layer. In other words, the titanium material for hot rolling described later is obtained by attaching a base material to a surface layer and welding the periphery thereof, but in the subsequent hot rolling heating and heat treatment steps after cold rolling, the base material and the surface layer are formed. Diffusion occurs at the interface of the material, and when finally processed into a titanium composite, an intermediate layer is formed between the inner layer from the base material and the surface layer from the surface layer. This intermediate layer has a chemical composition different from the chemical composition of the base material. The intermediate layer is strongly bonded to the inner layer and the surface layer metal. Further, since a continuous element gradient is generated in the intermediate layer, the difference in strength between the inner layer and the surface layer can be alleviated, and cracking during processing can be suppressed.
又，中間層之厚度可利用EPMA或GDS來測定。若使用GDS則可作更詳細之測定。於GDS之情形下將表層作某種程度之研磨除去後，藉由進行自表面朝深度方向之GDS分析，可測定中間層之厚度。中間層係指將來自母材之增加含量(母材所不含之元素之情形下為其含量，母材中亦含之元素之情形下為來自母材之含量的增加部分)設為CMID，將表層部之增加含量的平均設為CAVE 時，於0<CMID≦0.8×CAVE之區域。 Further, the thickness of the intermediate layer can be measured by EPMA or GDS. More detailed measurements can be made if GDS is used. In the case of GDS, after the surface layer is removed by some degree of polishing, the thickness of the intermediate layer can be measured by performing GDS analysis from the surface in the depth direction. The intermediate layer is defined as the C MID from the increased content of the base material (the content of the element contained in the base material, the content of the element contained in the base material, and the increase from the content of the base material). When the average of the increased content of the surface layer portion is C AVE , it is in the region of 0 < C MID ≦ 0.8 × C AVE .
此一中間層之厚度係設為0.5μm以上。另一方面，中間層之厚度若是過大，則與其相應地表層之合金層變薄，而有無法表現效果之情形。因此，其上限宜設為15μm。 The thickness of this intermediate layer is set to 0.5 μm or more. On the other hand, if the thickness of the intermediate layer is too large, the alloy layer of the surface layer corresponding thereto becomes thin, and there is a case where the effect cannot be expressed. Therefore, the upper limit should be set to 15 μm.
本發明之熱軋用鈦材，係供給熱間加工之素材(扁胚、中胚、小胚等之鑄片)，熱間加工後，再因應必要施以冷間加工、熱處理等而加工成鈦複合材。以下，使用圖面說明本發明之熱軋用鈦材。又，以下之說明中，有關各元素之含量之「%」係指「質量%」。 The titanium material for hot rolling of the present invention is supplied with a material for hot intercalation processing (a cast piece of a flat embryo, a medium embryo, a small embryo, etc.), and is processed into a cold process, a heat treatment, etc. Titanium composite. Hereinafter, the titanium material for hot rolling of the present invention will be described with reference to the drawings. In the following description, the "%" of the content of each element means "% by mass".
第3圖係將母材(鈦矩形鑄片、扁胚)6與表層材(鈦板)7於真空中熔接而貼合予以示意性表示之說明圖，第4圖係將不僅於母材(鈦矩形鑄片、扁胚)6之表面(輥軋面)且於側面(輥軋面以外之面)亦將表層材(鈦板)7、8熔接而貼合予以示意性表示之說明圖。 Fig. 3 is an explanatory view schematically showing a base material (titanium rectangular cast piece, flat blank) 6 and a surface layer (titanium plate) 7 welded together in a vacuum, and Fig. 4 is a view not only on the base material ( The surface (rolled surface) of the titanium rectangular slab and the flat slab 6 is welded to the side surface (the surface other than the rolled surface), and the surface materials (titanium plates) 7 and 8 are also welded and bonded to each other to be schematically shown.
本發明中，如第3、4圖所示，於母材即扁胚6之表面貼合含有可表現耐氧化性之合金元素的鈦板7、8後，利用熱軋包層法接合而將鈦複合材1、2之表層合金化。 In the present invention, as shown in Figs. 3 and 4, the titanium plates 7 and 8 containing an alloying element capable of exhibiting oxidation resistance are bonded to the surface of the flat metal 6 which is a base material, and then joined by a hot rolling cladding method. The surface layers of the titanium composites 1 and 2 are alloyed.
於製造第1圖所示之鈦複合材1的情形下， 如第3圖所示可只於扁胚6之單面在真空中貼合鈦板7即可，而於扁胚6之另一單面上不貼附鈦板7即行熱軋。 In the case of manufacturing the titanium composite 1 shown in Fig. 1, As shown in Fig. 3, the titanium plate 7 may be bonded to the single side of the flat blank 6 in a vacuum, and the titanium plate 7 may be attached to the other side of the flat blank 6 without hot rolling.
如第4圖所示，除扁胚6之單面以外又可於另一單面上貼合鈦板7。藉此，如上所述可抑制熱軋步驟中之熱軋瑕疵的發生。 As shown in Fig. 4, in addition to the single side of the flat blank 6, the titanium plate 7 can be attached to the other side. Thereby, the occurrence of hot rolling in the hot rolling step can be suppressed as described above.
再者，於製造第2圖所示之鈦複合材2的情形下，如第4圖所示，於扁胚6之兩個輥軋面貼合含有合金元素之板即可。 Further, in the case of producing the titanium composite material 2 shown in Fig. 2, as shown in Fig. 4, a plate containing an alloy element may be bonded to the two rolled surfaces of the flat blank 6.
再者，如第4圖所示，可針對熱軋時成為邊緣側之扁胚6的側面，亦與輥軋面相同於真空中貼合同一規格之鈦板8進行熔接。 Further, as shown in Fig. 4, the side surface of the flat blank 6 which is the edge side during hot rolling can be welded to the titanium plate 8 which is the same as the rolled surface in the vacuum.
亦即，於熱軋中，通常扁胚6被施加輾軋，因而扁胚6之側面之至少一部分將迂迴至熱軋板之表面側。因此，若扁胚6之側面的表層之組織粗大，或是存在多數之缺陷時，則熱軋板之寬度方向的兩端附近之表面會有發生表面瑕疵之可能性。因此，藉由於扁胚6之側面亦將鈦板8於真空中貼合及熔接，可有效防止熱軋板之寬度方向的兩端附近之表面發生表面瑕疵。 That is, in the hot rolling, usually, the flat embryo 6 is subjected to rolling, and at least a part of the side surface of the flat blank 6 is drawn back to the surface side of the hot rolled sheet. Therefore, if the surface layer of the side surface of the flat blank 6 is coarse or there are many defects, the surface of the hot rolled sheet near the both ends in the width direction may have a surface flaw. Therefore, since the titanium plate 8 is bonded and welded in a vacuum in the side surface of the flat blank 6, it is possible to effectively prevent surface flaws on the surface near the both ends in the width direction of the hot rolled sheet.
又，熱軋時扁胚6之側面的迂迴量，依製造方法雖有不同，但通常為20~30mm之程度，因此無須於扁胚6之側面全面貼附鈦板8，於與依製造方法之迂迴量相當的部分貼附鈦板8即可。 Moreover, the amount of twist of the side surface of the flat blank 6 during hot rolling varies depending on the manufacturing method, but is usually about 20 to 30 mm, so that it is not necessary to completely attach the titanium plate 8 to the side of the flat embryo 6, and the manufacturing method is A considerable amount of the back is attached to the titanium plate 8.
於製造鈦複合材1、2時，為了除去因熱軋所形成之氧化層，熱軋後乃經由噴砂-酸洗之步驟而進行製造。然而，於此一步驟之際，若是熱軋包層所形成之表層遭到除去，則無法表現耐氧化性。 When the titanium composite materials 1 and 2 are produced, in order to remove the oxide layer formed by hot rolling, the hot rolling is performed by a sandblasting-pickling step. However, at this step, if the surface layer formed by the hot-rolled cladding is removed, the oxidation resistance cannot be exhibited.
又，鈦複合材1、2之表層的厚度若是變得過薄，則將變得無法表現目標之耐氧化性。另一方面，表層之厚度若是過厚，則相應地製造成本會增加。由於鈦複合材1、2具有與使用目的配合之表層的厚度即可，因此作為素材使用之鈦板7、8的厚度並無特別限定之必要，然以扁胚6之厚度的5~40%之範圍為宜。 Moreover, if the thickness of the surface layer of the titanium composite materials 1 and 2 becomes too thin, the target oxidation resistance will not be exhibited. On the other hand, if the thickness of the surface layer is too thick, the manufacturing cost will increase accordingly. Since the titanium composite materials 1 and 2 have a thickness of the surface layer to be used for the purpose of use, the thickness of the titanium plates 7 and 8 used as the material is not particularly limited, but the thickness of the flat embryo 6 is 5 to 40%. The scope is appropriate.
作為表層材(鈦板)，係使用於前述鈦複合材之表層的項目中所說明之具有特定化學組成之鈦板。特別令人滿意的是，有關鈦板之化學組成，為了抑制熱軋所致之板破斷，以與上述母材相同之成分為基本，將其調整成在其中含有特定之元素的成分。 As the surface layer (titanium plate), a titanium plate having a specific chemical composition described in the item of the surface layer of the above-mentioned titanium composite material is used. It is particularly preferable that the chemical composition of the titanium plate is adjusted to a component containing a specific element in order to suppress breakage of the plate due to hot rolling, in the same manner as the above-mentioned base material.
作為母材，係使用前述鈦複合材之內層的項目所說明之工業用純鈦或鈦合金。特別是母材宜使用直接鑄造扁胚。直接鑄造扁胚，可為表面之至少一部分形成有熔融再凝固層者。又，也可為於直接鑄造扁胚之表面實施熔融再凝固處理時添加特定之元素，而形成有熔融再凝固層者，此熔融再凝固層具有與直接鑄造扁胚之板厚中心部不同的化學組成。 As the base material, industrial pure titanium or a titanium alloy described in the item of the inner layer of the titanium composite material is used. In particular, the base material should be directly cast flat embryos. A direct cast flat embryo can be formed by melting a resolidified layer on at least a portion of the surface. Further, in the case where the surface of the directly cast flat embryo is subjected to a melt re-solidification treatment, a specific element is added to form a molten re-solidified layer having a different thickness from the center portion of the directly cast flat embryo. chemical components.
於扁胚6之當作輥軋面的表面上，貼合含有合金元素之鈦板7後，於真空容器內，至少將周圍以熔接部9熔接，藉而將扁胚6與鈦板7、8之間真空密閉而與外氣遮斷，並藉由輥軋而將扁胚6與鈦板7、8貼合。於扁胚6上貼合鈦板7、8後接合之熔接部，係以將扁胚6與鈦板7、8之界面自大氣遮斷的方式，例如如第3、4圖所示般之將全周熔接。 On the surface of the flattened blank 6 as a rolled surface, after bonding the titanium plate 7 containing the alloying element, at least the surrounding portion is welded by the welded portion 9 in the vacuum container, whereby the flat blank 6 and the titanium plate 7 are The vacuum is sealed between the 8 and the outside air, and the flat embryo 6 is bonded to the titanium plates 7, 8 by rolling. The welded portion to which the titanium plates 7 and 8 are bonded to the flat blank 6 is formed by blocking the interface between the flat blank 6 and the titanium plates 7 and 8 from the atmosphere, for example, as shown in FIGS. 3 and 4. The whole week will be welded.
鈦為活性金屬，因此若放置於大氣中則表面將形成強固之鈍態皮膜。將此表面部之氧化濃化層除去不可能。然而，與不鏽鋼等不同，氧易於固溶於鈦，因此若是在真空中密閉而於自外部不供給氧的狀態下被加熱，則表面之氧會擴散至內部而固溶，因此表面形成之鈍態皮膜會消滅。因此，扁胚6與其表面之鈦板7、8，可於其間不產生夾雜物等之情形下，由熱軋包層法完全密接。 Titanium is an active metal, so if placed in the atmosphere, the surface will form a strong passive film. It is impossible to remove the oxidized concentrated layer on the surface portion. However, unlike stainless steel or the like, oxygen is easily dissolved in titanium. Therefore, if it is sealed in a vacuum and heated without supplying oxygen from the outside, oxygen on the surface diffuses to the inside and solidifies, so the surface is blunt. The membrane will be destroyed. Therefore, the flat blank 6 and the titanium plates 7 and 8 on the surface thereof can be completely adhered by the hot rolling cladding method without causing inclusions or the like therebetween.
再者，作為扁胚6若使用鑄造後原狀之扁胚，起因於凝固時生成之粗大的結晶粒，於其後之熱軋步驟中會發生表面瑕疵。相對於此，如本發明般之若於扁胚6之輥軋面貼合鈦板7、8，則因貼合之鈦板7具有微細之組織，因此還可抑制熱軋步驟之表面瑕疵。 Further, when the flat embryo 6 is used as the original embryo after casting, it is caused by coarse crystal grains generated during solidification, and surface flaws occur in the subsequent hot rolling step. On the other hand, if the titanium plates 7 and 8 are bonded to the rolled surface of the flat blank 6 as in the present invention, since the bonded titanium plate 7 has a fine structure, the surface flaw of the hot rolling step can be suppressed.
熱軋用鈦材之母材，通常，係將錠利用分解形成為扁胚或小胚形狀後，再切削精整而製造。又，近年以來，也有於錠製造時，製造可直接熱軋之矩形扁胚供熱軋之情形。利用分解而製造之情形下，因分解之故表面形成為較平坦，而易於將含合金元素之素材較均一地散布，易於使合金相之元素分布均一。 The base material of the titanium material for hot rolling is usually produced by decomposing the ingot into a flat embryo or a small embryo shape, and then cutting and finishing. Further, in recent years, there has been a case where a rectangular flat embryo which can be directly hot rolled is produced for hot rolling in the production of an ingot. In the case of manufacturing by decomposition, the surface is formed to be relatively flat due to decomposition, and it is easy to uniformly distribute the material containing the alloying elements, and it is easy to make the elemental distribution of the alloy phase uniform.
另一方面，於鑄造時若以直接製造成熱軋用素材之形狀的鑄塊(直接鑄造扁胚)作為母材使用的情形下，因可省略切削精整步驟，故可更價廉地製造。又，於鑄塊製造後，將其表面切削精整後再予使用的話，可期待經由分解而製造之情形下相同之效果。本發明中，若於表層安定地形成有合金層即可，可配合狀況選擇適切之素材。 On the other hand, in the case where an ingot (direct cast flat blank) which is directly formed into a shape of a material for hot rolling is used as a base material at the time of casting, since the cutting finishing step can be omitted, it can be manufactured more inexpensively. . Moreover, after the ingot is manufactured and the surface is cut and finished, it is expected to have the same effect in the case of production by decomposition. In the present invention, if an alloy layer is formed in the surface layer stably, an appropriate material can be selected in accordance with the condition.
較佳的是，例如組合完成扁胚並將其周圍熔接後，予以加熱於700~850℃進行10~30%之接合輥軋，而後以β域溫度進行3~10小時加熱使母材成分擴散至表層部之後，再進行熱軋。這是因為，藉由於β域溫度下進行熱軋，變形阻力變低而易於輥軋所致。 Preferably, for example, after the flat embryos are combined and welded, they are heated at 700 to 850 ° C for 10 to 30% of the joining and rolling, and then heated at a β domain temperature for 3 to 10 hours to diffuse the base material. After the surface layer, hot rolling is performed. This is because, by hot rolling at the temperature of the β domain, the deformation resistance is lowered and it is easy to roll.
作為母材使用之直接鑄造扁胚，可為表面之至少一部分形成有熔融再凝固層者。又，也可為於直接鑄造扁胚之表面實施熔融再凝固處理時添加特定之元素，而形成有熔融再凝固層者，此熔融再凝固層具有與直接鑄造扁胚之板厚中心部不同的化學組成。以下，針對熔融再凝固處理詳細說明。 A direct-cast flat embryo used as a base material may be formed by melting and re-solidifying a layer on at least a part of the surface. Further, in the case where the surface of the directly cast flat embryo is subjected to a melt re-solidification treatment, a specific element is added to form a molten re-solidified layer having a different thickness from the center portion of the directly cast flat embryo. chemical components. Hereinafter, the melt resolidification treatment will be described in detail.
第5~7圖均是表示熔融再凝固之方法的說明圖。作為將熱軋用鈦材之母材表面予以熔融再凝固的方法，包括雷射加熱，電漿加熱、感應加熱、電子射束加熱等，任一種方法均屬可行。特別是於電子射束加熱之情形下，由於係在高真空中進行，於熔融再凝固處理時，即使該層中形成孔隙等，由於為真空，因此可藉由而後之輥軋而壓著無害化。 Figs. 5 to 7 are explanatory views each showing a method of melting and resolidifying. As a method of melting and resolidifying the surface of the base material of the titanium material for hot rolling, including laser heating, plasma heating, induction heating, electron beam heating, etc., any method is feasible. In particular, in the case of electron beam heating, since it is carried out in a high vacuum, even if pores or the like are formed in the layer during the melt resolidification treatment, since it is a vacuum, it can be pressed by the subsequent rolling and is harmless. Chemical.
再者，由於能量效率高，即使將大面積處理也可深層地予以熔融，因此特別適於鈦複合材之製造。於真空中熔融之情形下的真空度，令人滿意的是3×10-3Torr以下之更高的真空度。又，有關將熱軋用鈦材之表層熔融再凝固的次數，並無特別限制。惟，次數愈多則處理時間愈長而導致成本增加，因此令人滿意的是1次至2次。 Further, since the energy efficiency is high, it can be deeply melted even if it is treated in a large area, and therefore it is particularly suitable for the production of a titanium composite material. The degree of vacuum in the case of melting in a vacuum is satisfactorily a higher degree of vacuum of 3 × 10 -3 Torr or less. Moreover, the number of times of melting and resolidifying the surface layer of the titanium material for hot rolling is not particularly limited. However, the more the number of times, the longer the processing time leads to an increase in cost, so that it is satisfactory one to two times.
表層之熔融再凝固法，於為矩形之扁胚之情形下，係如第5圖所示般之實施。具體言之，針對矩形扁胚10之外表面之中，至少成為熱軋步驟之輥軋面(與熱軋輥相接之面)的寬幅之二面10A、10B照射電子射束，只令該面之表面層熔融。此處首先針對該二面10A、10B中一方之面10A實施。 The melt re-solidification method of the surface layer is carried out as shown in Fig. 5 in the case of a rectangular flat embryo. Specifically, for the outer surface of the rectangular flat blank 10, at least the wide sides 10A, 10B which are the rolling surfaces of the hot rolling step (the surface in contact with the hot rolling rolls) are irradiated with electron beams, and only the The surface layer of the surface is melted. Here, first, the surface 10A of one of the two faces 10A and 10B is implemented.
此處，如第5圖所示，對於矩形鑄片10之面10A的一台電子射束照射槍12所為之電子射束的照射區域14之面積，通常較待照射面10A之全面積額外地小出甚多，因此，實際上通常係一面將電子射束照射槍12連續移動或是將矩形鑄片10連續移動，一面進行電子射束 照射。此一照射區域，藉由調整電子射束之焦點、或是使用電磁透鏡令小射束高頻振動(Oscillation)而形成射束流，藉而可調整其形狀或面積。 Here, as shown in Fig. 5, the area of the irradiation region 14 of the electron beam which is directed to the electron beam irradiation gun 12 of the face 10A of the rectangular cast piece 10 is usually additionally larger than the entire area of the face 10A to be irradiated. There is a lot of smallness. Therefore, in practice, the electron beam irradiation gun 12 is continuously moved or the rectangular casting piece 10 is continuously moved while the electron beam is being carried out. Irradiation. In this illumination region, the beam current is formed by adjusting the focus of the electron beam or by using an electromagnetic lens to make a small beam of Oscillation, whereby the shape or area can be adjusted.
另外，如第5圖中之箭頭A所示，針對將電子射束照射槍12連續移動者，進行以下之說明。又，電子射束照射槍之移動方向並未特別限定，一般係沿矩形鑄片10之長度方向(通常為鑄造方向D)或寬度方向(通常為與鑄造方向D垂直之方向)連續移動，就前述照射區域14之寬度W(圓形射束或射束流之情形下，直徑W)連續作帶狀照射。進而針對與其相鄰之未照射帶狀區域則於逆向(或同向)一面將照射槍12連續移動一面帶狀地進行電子射束照射。又依情況之別，也可使用複數個照射槍，同時就複數個區域同時進行電子射束照射。第5圖中係表示沿矩形鑄片10之長度方向(通常為鑄造方向D)將矩形射束連續移動之情形。 Further, as shown by an arrow A in Fig. 5, the following description will be made for the case where the electron beam irradiation gun 12 is continuously moved. Further, the moving direction of the electron beam irradiation gun is not particularly limited, and generally moves continuously along the longitudinal direction of the rectangular cast piece 10 (usually in the casting direction D) or in the width direction (usually in the direction perpendicular to the casting direction D). The width W of the aforementioned irradiation region 14 (in the case of a circular beam or a beam current, the diameter W) is continuously irradiated in a strip shape. Further, the irradiated gun 12 is continuously moved in the opposite direction (or the same direction) with respect to the adjacent unilluminated strip-shaped region, and the electron beam irradiation is performed in a strip shape. Depending on the situation, a plurality of illuminating guns may be used, and electron beam irradiation may be simultaneously performed on a plurality of regions. In Fig. 5, the case where the rectangular beam is continuously moved in the longitudinal direction of the rectangular cast piece 10 (usually in the casting direction D) is shown.
藉由如此般之表層加熱處理步驟對矩形鈦鑄片10之表面(面10A)照射電子射束，將其表面加熱成熔融狀的話，如第6圖之中央偏左所示，矩形鈦鑄片10之面10A的表面層，係以響應入熱量之深度被最大地熔融。然而，相對電子射束之照射方向自垂直方向之深度如第7圖所示並非一定，電子射束照射之中央部為最大深度，愈往帶狀之端部其厚度愈是減少而成為下凸之彎曲形狀。 When the surface (face 10A) of the rectangular titanium slab 10 is irradiated with an electron beam by such a surface heat treatment step, and the surface thereof is heated to be molten, as shown in the center of the sixth figure, the rectangular titanium slab is shown. The surface layer of 10A of 10 is most melted in response to the depth of heat input. However, the depth from the vertical direction of the irradiation direction of the electron beam is not constant as shown in Fig. 7, and the central portion of the electron beam irradiation is the maximum depth, and the thickness of the end portion of the strip is reduced to become the lower convex portion. The curved shape.
又，較其熔融層16更靠鑄片內部側之區域亦 然，因電子射束照射所帶來之熱影響而溫度上升，成為純鈦之β變態點以上之溫度的部分(熱影響層=HAZ層)變態成β相。如是般之因表層加熱處理步驟之電子射束照射所帶來的熱影響而變態成β相之區域亦然，與熔融層16之形狀相同，成為下凸之彎曲形狀。 Moreover, the area on the inner side of the cast piece is also larger than the molten layer 16 However, the temperature rises due to the influence of the heat of the electron beam irradiation, and the temperature (the heat-affected layer=HAZ layer) which is a temperature higher than the β-deformation point of pure titanium is transformed into the β phase. In the same manner, the region which is transformed into the β phase due to the thermal influence by the electron beam irradiation in the surface heating treatment step is the same as the shape of the molten layer 16 and has a curved shape which is convex downward.
藉由將表層與含有目的之合金元素的素材一起進行熔融再凝固，可將熱軋用素材表層合金化，而形成與母材不同之化學組成的合金層。作為此時所用之素材，可使用粉末、小片、線材、薄膜、切屑、網狀物中之一種以上。有關熔融前配置之材料之成分以及量，係以與素材表面一起熔融凝固後之元素濃化區域的成分成為目標成分之方式規定。 By melting and resolidifying the surface layer together with the material containing the intended alloying element, the surface layer for hot rolling can be alloyed to form an alloy layer having a chemical composition different from that of the base material. As the material used at this time, one or more of a powder, a small piece, a wire, a film, a chip, and a mesh can be used. The component and the amount of the material disposed before the melting are defined as a component of the element-concentrated region which is melt-solidified together with the surface of the material as a target component.
惟，此一添加之素材若是過大，則會成為合金成分的偏析之原因。而且，合金成分之偏析若是存在，將無法充分發揮所期望之性能，或是造成劣化提早發生。因此，重要的是鈦母材表面之被加熱部位於熔融狀態之期間之中，合金素材成為熔融終了之尺寸。又，重要的是於考慮特定時間之熔融部之形狀及寬廣程度後，將上述合金素材預先均等地配置於鈦母材表面。然而，在使用電子射束將照射位置連續移動之情形下，由於熔融部係與熔融之鈦及合金一起連續移動一面被攪拌，因此合金素材不一定有非得事先連續配置之必要。此外，當然必須要避免使用具有較鈦之熔點為極端高的熔點之合金素材。 However, if the material added is too large, it will cause segregation of the alloy composition. Further, if the segregation of the alloy component is present, the desired performance may not be sufficiently exhibited, or the deterioration may occur early. Therefore, it is important that the heated portion of the surface of the titanium base material is in a molten state, and the alloy material becomes the size of the melting end. Further, it is important to arrange the alloy material in advance on the surface of the titanium base material in consideration of the shape and the width of the molten portion at a specific time. However, in the case where the irradiation position is continuously moved by using the electron beam, since the molten portion is stirred while continuously moving together with the molten titanium and the alloy, the alloy material does not necessarily have to be continuously arranged in advance. In addition, it is of course necessary to avoid the use of alloy materials having an extremely high melting point than the melting point of titanium.
熔融再凝固處理後，宜以100℃以上且小於 500℃之溫度保持1小時以上。熔融再凝固後，若急劇冷卻，則因凝固時之應變而表層部有發生微細破裂之虞。於而後之熱軋步驟或冷軋步驟中，以該微細之破裂為起點，會有如同表層之剝離發生、局部合金層薄化部位發生等之特性劣化之虞。又，因微細之破裂以致內部氧化時，則有以酸洗步驟予以除去之必要，而會進一步減少合金層之厚度。藉由以上述之溫度進行保持，可抑制表面之微細的破裂。又，若是此一溫度，即使是大氣中保持也幾乎不會發生大氣氧化。 After melting and resolidification treatment, it should be above 100 ° C and less than The temperature at 500 ° C is maintained for more than 1 hour. After melting and re-solidification, if it is rapidly cooled, the surface layer portion is slightly broken due to the strain at the time of solidification. In the subsequent hot rolling step or cold rolling step, the fine crack is used as a starting point, and the characteristics such as peeling of the surface layer and occurrence of a thinned portion of the local alloy layer occur. Further, when the internal cracking occurs due to fine cracking, it is necessary to remove it by the pickling step, and the thickness of the alloy layer is further reduced. By holding at the above temperature, fine cracking of the surface can be suppressed. Moreover, at this temperature, atmospheric oxidation hardly occurs even if it is maintained in the atmosphere.
藉由於具備由熔融再凝固處理所形成之表層部的母材表面上貼附含有特定之合金成分的鈦板，可製造熱軋用鈦材。 The titanium material for hot rolling can be produced by attaching a titanium plate containing a specific alloy component to the surface of the base material having the surface layer portion formed by the melt resolidification treatment.
熱軋用鈦材宜藉由熱軋包層法將周圍預先經熔接之扁胚6與鈦板7、8接合。 The titanium material for hot rolling is preferably joined to the titanium plates 7, 8 by a hot-rolled cladding method.
如第3、4圖所示，於扁胚6之表層貼附含有表現特性之合金元素的鈦板7、8後，利用熱軋包層法予以接合，藉而將鈦複合材之表層合金化。亦即，對於扁胚6之當作輥軋面的表面上，貼合含有合金元素之鈦板7，較佳的是於真空容器內，至少將周圍以熔接部9熔接，藉而將扁胚6與鈦板7之間真空密閉，並藉由輥軋將扁胚6與鈦板7貼合。於扁胚6上將鈦板7貼合之熔接，係以扁胚6與鈦板7之間大氣不侵入之方式，例如如第3、4圖 所示般之將全周熔接。 As shown in Figs. 3 and 4, the titanium plates 7 and 8 containing alloying elements having characteristics are attached to the surface layer of the flat embryo 6, and then joined by a hot-rolled cladding method to alloy the surface layer of the titanium composite material. . That is, the titanium plate 7 containing the alloying elements is attached to the surface of the flat surface of the flat blank 6 as a rolled surface, preferably in a vacuum container, at least the surrounding portion is welded by the welded portion 9, thereby the flat embryo 6 and the titanium plate 7 are vacuum-sealed, and the flat blank 6 is bonded to the titanium plate 7 by rolling. The titanium plate 7 is welded to the flat embryo 6 in a manner such that the atmosphere between the flat embryo 6 and the titanium plate 7 does not intrude, for example, as shown in Figs. It will be welded throughout the week as shown.
鈦為活性金屬，因此若放置於大氣中則表面將形成強固之鈍態皮膜。將此表面部之氧化濃化層除去不可能。然而，與不鏽鋼等不同，鈦之中氧易於固溶，若是真空中密閉而於自外部不供給氧的狀態下被加熱，則表面之氧會擴散至內部而固溶，因此表面形成之鈍態皮膜會消滅。因此，扁胚6與其表面之鈦板7，可於其間不產生夾雜物等之情形下，由熱軋包層法完全密接。 Titanium is an active metal, so if placed in the atmosphere, the surface will form a strong passive film. It is impossible to remove the oxidized concentrated layer on the surface portion. However, unlike stainless steel and the like, oxygen is easily dissolved in titanium, and if it is sealed in a vacuum and heated without supplying oxygen from the outside, oxygen on the surface diffuses to the inside and solidifies, so that the surface is formed into a passive state. The film will be destroyed. Therefore, the flat blank 6 and the titanium plate 7 on the surface thereof can be completely adhered by the hot rolling cladding method without causing inclusions or the like therebetween.
再者，作為扁胚6若是使用鑄造後原狀之扁胚，則起因於凝固時生成之粗大的結晶粒，於而後之熱軋步驟中會發生表面瑕疵。相對於此，如本發明般之若於扁胚6之輥軋面貼合鈦板7，則因貼合之鈦板7具有微細之組織，故而還可抑制熱軋步驟中之表面瑕疵。 Further, if the flat embryo 6 is used as a raw embryo after casting, it is caused by coarse crystal grains which are formed during solidification, and surface flaws occur in the subsequent hot rolling step. On the other hand, when the titanium plate 7 is bonded to the rolled surface of the flat blank 6 as in the present invention, since the bonded titanium plate 7 has a fine structure, the surface flaw in the hot rolling step can be suppressed.
如第3圖所示，不只於扁胚6之單面，也可於其兩面貼合鈦板7。藉此，如上述般可抑制熱軋步驟中之熱軋瑕疵的發生。熱軋之中，通常因扁胚6被輾軋過，扁胚6之側面的至少一部分會迂迴至熱軋板之表面側。因此，若是扁胚6之側面的表層之組織粗大，或是有多數之缺陷存在，則熱軋板之寬度方向的兩端附近之表面會有發生表面瑕疵之可能性。因此，如第4圖所示，宜於熱軋時之成為邊緣側的扁胚6之側面，亦與輥軋面相同地貼合同一規格之鈦板8予以熔接。藉此，可有效防止熱軋板之寬度方向之兩端附近的表面發生表面瑕疵。此一熔接宜在真空中進行。 As shown in Fig. 3, not only the single side of the flat blank 6, but also the titanium plate 7 may be bonded to both sides thereof. Thereby, the occurrence of hot rolling in the hot rolling step can be suppressed as described above. In the hot rolling, usually, the flat embryo 6 is rolled, and at least a part of the side surface of the flat blank 6 is drawn back to the surface side of the hot rolled sheet. Therefore, if the surface layer of the side surface of the flat blank 6 is coarse or has many defects, the surface near the both ends in the width direction of the hot rolled sheet may have a surface flaw. Therefore, as shown in Fig. 4, it is preferable to form the side surface of the flat blank 6 on the edge side at the time of hot rolling, and also to splicing the titanium plate 8 of a contract type similarly to the rolled surface. Thereby, it is possible to effectively prevent surface flaws on the surface near both ends in the width direction of the hot rolled sheet. This fusion is preferably carried out in a vacuum.
又，熱軋時扁胚6之側面迂迴的量，雖依製造方法而不同，通常為20~30mm程度，因此並無在扁胚6之側面全面貼附鈦板8之必要，只在相當於依據製造方法之迂迴量的部分貼附鈦板8即可。熱軋以降，藉由進行高溫長時間退火，可將由來自母材之成分含入鈦複合材之內部。可例示的是例如700~900℃下進行30小時之熱處理。 Further, the amount of the side back of the flat embryo 6 during hot rolling differs depending on the manufacturing method, and is usually about 20 to 30 mm. Therefore, it is not necessary to completely attach the titanium plate 8 to the side of the flat embryo 6, and it is only equivalent. The titanium plate 8 may be attached to the portion of the manufacturing method. By hot rolling, the composition from the base material can be contained in the interior of the titanium composite by performing high-temperature annealing for a long time. For example, a heat treatment for 30 hours at 700 to 900 ° C can be exemplified.
將扁胚6與鈦板7、8在真空中熔接之方法，包括電子射束熔接或電漿熔接等等。特別令人滿意是電子射束熔接於高真空下實施，藉而可將扁胚6與鈦板7、8之間設為高真空。令人滿意的是，將鈦板7、8於真空中熔接之情形下的真空度，設為3×10-3Torr以下之更高的真空度。 A method of welding the flat blank 6 and the titanium plates 7, 8 in a vacuum, including electron beam welding or plasma welding, and the like. It is particularly desirable to carry out the electron beam welding under high vacuum, whereby a high vacuum can be set between the flat blank 6 and the titanium plates 7, 8. Desirably, the degree of vacuum in the case of the titanium plates 7,8 fused in vacuo, to the following 3 × 10 -3 Torr of a higher degree of vacuum.
又，扁胚6與鈦板7之熔接，不一定非得要在真空容器內進行，例如，可於鈦板7之內部預先設置真空吸引用孔，將鈦板7與扁胚6重合後，一面利用真空吸引孔將扁胚6與鈦板7之間抽真空，一面將扁胚6與鈦板7熔接，且於熔接後封閉真空吸引孔。 Further, the welding of the flat blank 6 and the titanium plate 7 does not necessarily have to be performed in a vacuum container. For example, a vacuum suction hole may be provided in advance in the titanium plate 7, and the titanium plate 7 and the flat blank 6 may be overlapped. The vacuum is used to evacuate the flat blank 6 and the titanium plate 7, and the flat blank 6 is welded to the titanium plate 7, and the vacuum suction hole is closed after welding.
作為包層乃於扁胚6之表面使用具有目的之合金元素的鈦板7、8，利用熱軋包層於鈦複合材1、2之表層形成合金層的情形下，表層之厚度或化學成分係依存於貼合前的鈦板7、8之厚度或合金元素之分布。當然，於製造鈦板7、8時，為了獲得最終必要之強度與延性，係於真空氛圍等之中實施退火處理，因此造成界面處之擴 散，而使界面附近於深度方向生成濃度梯度。 As the cladding, the titanium plates 7 and 8 having the intended alloying elements are used on the surface of the flat blank 6, and the thickness or chemical composition of the surface layer is formed by hot-rolling cladding to form an alloy layer on the surface layers of the titanium composites 1 and 2. It depends on the thickness of the titanium plates 7, 8 before the bonding or the distribution of the alloying elements. Of course, in the manufacture of the titanium plates 7, 8, in order to obtain the final necessary strength and ductility, annealing treatment is performed in a vacuum atmosphere or the like, thereby causing expansion at the interface. Disperse, and a concentration gradient is generated in the depth direction near the interface.
然而，最終退火步驟所造成之元素的擴散距離為數μm左右，並非為合金層之厚度整體擴散，對於特別是特性表現有所重要之表層附近的合金元素之濃度沒有影響。 However, the diffusion distance of the element caused by the final annealing step is about several μm, which is not the overall diffusion of the thickness of the alloy layer, and has no effect on the concentration of the alloying element in the vicinity of the surface layer which is particularly important for the characteristic performance.
因此，鈦板7、8整體之合金成分的均一性係與特性之安定的表現息息相關。於熱軋包層之情形下，因可使用以製品製造之鈦板7、8，故板厚精度不消說，合金成分之偏析也易於控制，可製造具備表層之鈦複合材1、2，而此表層於製造後具有均一之厚度及化學成分，可表現安定之特性。 Therefore, the uniformity of the alloy composition of the titanium plates 7 and 8 as a whole is closely related to the performance of the stability of the characteristics. In the case of the hot-rolled cladding, since the titanium plates 7 and 8 manufactured by the products can be used, the thickness accuracy of the alloy is not easily controlled, and the segregation of the alloy components can be easily controlled, and the titanium composite materials 1 and 2 having the surface layer can be manufactured. This surface layer has a uniform thickness and chemical composition after manufacture, and can exhibit stable properties.
又，如上所述，鈦複合材1、2之表層與內層5之間不產生夾雜物，因此除了具有密接性以外，也不會成為破裂或疲勞等之起點。 Further, as described above, since no inclusions are formed between the surface layers of the titanium composite materials 1 and 2 and the inner layer 5, they do not become a starting point of cracking or fatigue, etc., in addition to the adhesion.
將於扁胚表面貼附鈦板而形成之合金層作為最終製品殘留此舉有所重要，因而有必要儘可能抑制氧化皮膜損耗或表面瑕疵所造成之表面層的除去。具體而言，在考慮生產中所使用之設備的特性或能力之後，將下述般之熱軋步驟上之技術方案最適化並適當地採用而予達成。 It is important that the alloy layer formed by attaching the titanium plate to the surface of the flat embryo is left as a final product residue, and it is therefore necessary to suppress the loss of the oxide film or the surface layer caused by the surface flaw as much as possible. Specifically, after considering the characteristics or capabilities of the equipment used in the production, the technical solutions on the hot rolling step described below are optimized and appropriately employed.
將熱軋用素材加熱時，藉由進行低溫短時間加熱可將 氧化皮膜損耗抑制為低，但因鈦材熱傳導小，若於扁胚內部為低溫狀態下進行熱軋，還會有內部易於發生破裂之缺點，因此乃配合使用之加熱爐之性能或特性最適化以將皮膜之發生抑制於最小限度。 When heating the material for hot rolling, it can be heated by low temperature for a short time. Oxidation film loss suppression is low, but due to the small heat conduction of the titanium material, if the inside of the flat embryo is hot-rolled at a low temperature, there is a disadvantage that the inside is prone to cracking, so that the performance or characteristics of the heating furnace to be used are optimized. In order to minimize the occurrence of the film.
熱軋步驟中亦然，若是表面溫度過高，以致通過時皮膜會多量生成，氧化皮膜損耗增大。另一方面，若是過低則氧化皮膜損耗雖然減少，但表面瑕疵變得易於發生，因此利用後續步驟之酸洗予以除去乃為必要，令人滿意的是以可抑制表面瑕疵之溫度範圍進行熱軋。因此，令人滿意的是以最適溫度範圍進行輥軋。又，輥軋中因鈦材之表面溫度降低，故而令人滿意的是輥軋中之輥冷卻設為最小限度，而抑制鈦材之表面溫度的降低。 Also in the hot rolling step, if the surface temperature is too high, a large amount of film is formed during the passage, and the oxide film loss is increased. On the other hand, if the oxide film loss is too low, the surface enthalpy becomes easy to occur, so it is necessary to remove it by pickling in a subsequent step, and it is desirable to carry out heat treatment by suppressing the temperature range of the surface enthalpy. Rolling. Therefore, it is desirable to perform rolling at an optimum temperature range. Further, since the surface temperature of the titanium material is lowered during the rolling, it is satisfactory that the cooling of the rolls during the rolling is minimized, and the decrease in the surface temperature of the titanium material is suppressed.
經熱軋之板，其表面有氧化層，因此具有以後續之步驟將氧化層除去之去皮膜步驟。鈦一般上主要是於噴砂後，以利用硝氟酸溶液之酸洗除去氧化層。又，依狀況而定，也有在酸洗後以磨石研磨而磨削表面之情形。去皮膜後，只要成為由來自熱軋用鈦材之母材及表層部之內層及表層所構成的2層或3層構造即可。 The hot rolled sheet has an oxide layer on its surface and thus has a step of removing the oxide layer in a subsequent step. Titanium is generally mainly used after sand blasting to remove the oxide layer by acid washing with a solution of nitric acid. Further, depending on the situation, there is a case where the surface is ground by grinding with a grindstone after pickling. After the film is removed, it may be a two-layer or three-layer structure composed of the inner layer and the surface layer of the base material and the surface layer portion of the titanium material for hot rolling.
熱軋步驟所生成之皮膜厚，因此通常於作為酸洗處理之前處理進行噴砂處理而除去表面之皮膜的一部 分之同時，會於表面形成裂痕，而於後續之酸洗步驟中造成液體浸透至裂痕，使得母材之一部分也一併除去。此時，進行不至於在母材表面生成裂痕之弱性噴砂處理乃為重要，有必要因應鈦材表面之化學成分選擇最適之噴砂條件。具體而言，例如藉由將適當之投射材之選擇或投射速度(以葉輪之轉速可調整)最適化，可選擇在母材上不生裂痕之條件。此等條件之最適化係因扁胚表面所貼附之鈦板的特性而異，因此預先將最適條件分別決定即可。 Since the film formed by the hot rolling step is thick, it is usually treated as a part of the film which is subjected to blasting treatment before the pickling treatment to remove the surface. At the same time, a crack is formed on the surface, and in the subsequent pickling step, the liquid is allowed to penetrate into the crack, so that a part of the base material is also removed. At this time, it is important to perform a weak blasting treatment which does not cause cracks on the surface of the base material, and it is necessary to select an optimum blasting condition in accordance with the chemical composition of the surface of the titanium material. Specifically, for example, by selecting an appropriate projection material or a projection speed (adjustable by the rotation speed of the impeller), a condition in which cracks are not generated on the base material can be selected. The optimization of these conditions differs depending on the characteristics of the titanium plate to which the surface of the flat embryo is attached. Therefore, the optimum conditions may be determined in advance.
以下，根據實施例將本發明更具體地說明，然本發明不受此等實施例之限定。 Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，於進行電子射束熔解並以角型鑄模鑄造而成之具有厚度200mm×寬度1000mm×長度4500mm的尺寸之第4圖所示之扁胚6的表面上，將含有Si、Nb、Ta至少一種以上的鈦合金板7於真空中熔接。於No.3及4之實施例中，於扁胚6之側面上亦將鈦合金板8於真空中熔接。而後，將熔接有鈦合金板7、8之扁胚6加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後再進行冷軋，而形成厚度1mm之鈦板，而後作為退火處理，於真空或惰性氣體氛圍中進行加熱至600~750℃並保持240分鐘之熱處 理，藉而製造表1所示之No.1~20之實施例(本發明例)以及比較例之供試驗材的鈦複合材2。 Specifically, on the surface of the flat blank 6 shown in FIG. 4 having a thickness of 200 mm × a width of 1000 mm × a length of 4500 mm, which is subjected to electron beam melting and casting by an angle mold, Si, Nb, At least one or more titanium alloy sheets 7 of Ta are welded in a vacuum. In the examples of Nos. 3 and 4, the titanium alloy sheet 8 was also welded in a vacuum on the side of the flat blank 6. Then, the flat embryo 6 to which the titanium alloy sheets 7, 8 were welded was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then the surface of the front and back were subjected to a peeling treatment by sand blasting and nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1 mm, and then heated as an annealing treatment in a vacuum or an inert gas atmosphere to 600 to 750 ° C for 240 minutes. The examples of Nos. 1 to 20 (inventive examples) shown in Table 1 and the titanium composite 2 for the test materials of Comparative Examples were produced.
自此等供試驗材1~21切出20mm×20mm之試驗片，將其表面與端部以# 400之砂紙研磨後，於700℃、750℃之各溫度下於大氣中曝露200小時，測定試驗前後之重量之變化，求得每個單位截面積之氧化增量。結果一併示於表1中。另，表1中之表層3、4之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 Test pieces of 20 mm × 20 mm were cut out from the test materials 1 to 21, and the surface and the end portion were ground with #400 sandpaper, and exposed to the atmosphere at 700 ° C and 750 ° C for 200 hours. The change in weight before and after the test was used to determine the oxidation increment per unit cross-sectional area. The results are shown together in Table 1. In addition, the elemental concentrations of the surface layers 3 and 4 in Table 1 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
表1之No.1之比較例，內層5含有工業用純鈦JIS2種，不具有表層3、4。因此，700℃之200小時的加熱下之氧化增量為40g/m2以上，750℃之200小時的加熱下之氧化增量為100g/m2以上，非常之高。 In the comparative example of No. 1 in Table 1, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and does not have the surface layers 3 and 4. Therefore, the oxidation increase under heating at 700 ° C for 200 hours is 40 g/m 2 or more, and the increase in oxidation under heating at 750 ° C for 200 hours is 100 g/m 2 or more, which is extremely high.
No.2之比較例，內層5含有工業用純鈦JIS2種，表層3、4雖含有Si，但其厚度為1μm非常之薄。又，中間層之厚度也非常之薄。因此，700℃之200小時的加熱下之氧化增量為40g/m2以上，750℃之200小時的加熱下之氧化增量為100g/m2以上，非常之高。 In the comparative example of No. 2, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, but the thickness thereof is very thin at 1 μm. Also, the thickness of the intermediate layer is also very thin. Therefore, the oxidation increase under heating at 700 ° C for 200 hours is 40 g/m 2 or more, and the increase in oxidation under heating at 750 ° C for 200 hours is 100 g/m 2 or more, which is extremely high.
No.3之本發明例，內層5含有工業用純鈦JIS1種，表層3、4含有Si。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 3, the inner layer 5 contains one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.4之本發明例，內層5含有工業用純鈦JIS2種，表層3、4含有Si。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 4, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.5之本發明例，內層5含有工業用純鈦JIS3種，表層3、4含有Si。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 5, the inner layer 5 contains three kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.6之本發明例，內層5含有工業用純鈦JIS3種，表層3、4含有Si。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 6, the inner layer 5 contains three kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.7之比較例，內層5含有工業用純鈦JIS2種，表層3、4雖含有Si，然表層3、4之Si含量卻高至0.7%。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性，然而熱軋時及冷軋時發生破裂，加工性劣化。 In the comparative example of No. 7, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, but the Si content of the surface layers 3 and 4 is as high as 0.7%. Therefore, the oxidation increase under heating for 200 hours at 700 ° C is 25 g / m 2 or less, and the oxidation increase under heating for 200 hours at 750 ° C is 70 g / m 2 or less, showing excellent oxidation resistance, but hot rolling Cracking occurs at the time of cold rolling and the workability is deteriorated.
No.8~21之本發明例，內層5含有工業用純鈦JIS2種，表層3、4含有Si、Nb、Ta、Al之一種以上。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 8 to 21, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain one or more of Si, Nb, Ta, and Al. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，No.22及23之本發明例，扁胚6係在進 行電子射束熔解並以角型鑄模鑄造後，於當作輥軋面之面經切削精整的具有厚度200mm×寬度1000mm×長度4500mm之尺寸的第3圖所示之扁胚6的表面上，將含有Si、Nb、Ta、Al至少一種以上的鈦合金板7於真空中熔接。又，No.24之本發明例，係在進行電子射束熔解並以角型鑄模鑄造後，將當作輥軋面之面經切削精整的具有厚度100mm×寬度1000mm×長度4500mm之尺寸的第4圖所示之扁胚6的表面切削精整後，將含有Si、Nb、Ta、Al至少一種以上的鈦合金板7於真空中熔接之。 Specifically, in the inventive example of Nos. 22 and 23, the flat embryo 6 is in progress. After the electron beam is melted and cast by the angle mold, the surface of the flat blank 6 shown in Fig. 3 having a thickness of 200 mm × a width of 1000 mm × a length of 4500 mm is cut and finished as a surface of the rolled surface. The titanium alloy sheet 7 containing at least one of Si, Nb, Ta, and Al is welded in a vacuum. Further, the present invention of No. 24 is an embodiment in which the electron beam is melted and cast in an angular mold, and the surface which is the surface of the rolled surface is cut and finished to have a thickness of 100 mm × a width of 1000 mm × a length of 4500 mm. After the surface of the flat blank 6 shown in Fig. 4 is cut and finished, at least one or more titanium alloy sheets 7 containing Si, Nb, Ta, and Al are welded in a vacuum.
而後，將熔接有鈦合金板7之扁胚6加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。而後再進行冷軋，而形成厚度1mm之鈦板，作為退火處理，係進行在真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理，藉而製造表2所示之No.22~24之本發明例之供試驗材即鈦複合材2。 Then, the flat embryo 6 to which the titanium alloy plate 7 was welded was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to de-peeling treatment on both the front and back surfaces by sand blasting and nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment is performed by heating to 600 to 700 ° C in a vacuum or an inert gas atmosphere for 240 minutes, thereby producing No. The titanium composite material 2 which is a test material of the present invention of 22 to 24 is used.
針對此等供試驗材，與實施例1相同地，求得每個單位截面積之氧化增量。結果一併示於表2中。又，表2中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 With respect to these test materials, the oxidation increment per unit cross-sectional area was determined in the same manner as in Example 1. The results are shown together in Table 2. Further, the elemental concentrations in the surface layer portion in Table 2 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
No.22之本發明例，內層5含有工業用純鈦JIS1種，表層3、4含有Si。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 22, the inner layer 5 contains one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.23之本發明例，內層5含有工業用純鈦JIS2種，表層3、4含有Nb。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 23, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Nb. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.24之本發明例，內層5含有工業用純鈦JIS3種，表層3、4含有Si及Al。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 24, the inner layer 5 contains three kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si and Al. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，在進行電漿電弧熔解並以角型鑄模鑄造後，於當作輥軋面之面經切削精整之具有厚度200mm×寬度1000mm×長度4500mm的尺寸之第4圖所示之扁胚6 的表面上，將含有各元素之鈦合金板於真空中熔接之。而後，將該扁胚加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。而後再進行冷軋，而形成厚度1mm之鈦板，作為退火處理，係進行在真空或惰性氣體氛圍中加熱至600~750℃並保持240分鐘之熱處理，藉而製造表3所示之No.25~27之實施例(本發明例)之供試驗材即鈦複合材2。 Specifically, after performing plasma arc melting and casting by angle molding, the flat surface shown in FIG. 4 having a thickness of 200 mm, a width of 1000 mm, and a length of 4500 mm is subjected to cutting and finishing as a surface of the rolling surface. Embryo 6 On the surface, a titanium alloy plate containing each element is welded in a vacuum. Then, the slab was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using blasting and nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment is performed by heating to 600 to 750 ° C in a vacuum or an inert gas atmosphere for 240 minutes, thereby producing No. The titanium composite material 2, which is a test material of the examples of 25 to 27 (inventive example).
針對此等供試驗材，與實施例1相同地，求得每個單位截面積之氧化增量。結果一併示於表3中。又，表3中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 With respect to these test materials, the oxidation increment per unit cross-sectional area was determined in the same manner as in Example 1. The results are shown together in Table 3. Further, the elemental concentrations in the surface layer portion in Table 3 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
No.25之本發明例，內層5含有工業用純鈦JIS1種，表層3、4含有Si，其厚度為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 25, the inner layer 5 contains one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.26之本發明例，內層5含有工業用純鈦JIS2種，表層3、4含有Nb，其厚度為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 26, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Nb, and the thickness thereof is 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.27之本發明例，內層5含有工業用純鈦JIS3種，表層3、4含有Si及Al，其厚度為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 27, the inner layer 5 contains three types of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si and Al, and have a thickness of 5 μm or more and a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，將鈦鑄塊以分解予以形成為矩形形狀後，於當作輥軋面之面經切削精整之具有厚度200mm×寬度1000mm×長度4500mm的尺寸之錠的表面經切削精整而成之第4圖所示之扁胚6的表面上，將含有合金元素之鈦合金板7於真空中熔接之。而後，將熔接有鈦合金板7之 扁胚6加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後進行冷軋，而形成厚度1mm之鈦板，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~750℃並保持240分鐘之熱處理，製造表4所示之No.28、29的本發明例之供試驗材即鈦複合材2。 Specifically, after the titanium ingot is formed into a rectangular shape by decomposition, the surface of the ingot having a thickness of 200 mm, a width of 1000 mm, and a length of 4,500 mm, which has been subjected to cutting and finishing as a surface of the rolled surface, is subjected to cutting and finishing. On the surface of the flat embryo 6 shown in Fig. 4, the titanium alloy sheet 7 containing the alloying elements was welded in a vacuum. Then, the titanium alloy plate 7 will be welded. The slab 6 was heated to 820 ° C and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using a blasting and a nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment is performed by heating to 600 to 750 ° C in a vacuum or an inert gas atmosphere for 240 minutes, and No. 28 and 29 shown in Table 4 are produced. The titanium composite material 2, which is a test material of the present invention.
針對此等供試驗材，與實施例1相同地，求得每個單位截面積之氧化增量。結果一併示於表4中。又，表4中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 With respect to these test materials, the oxidation increment per unit cross-sectional area was determined in the same manner as in Example 1. The results are shown together in Table 4. Further, the elemental concentrations in the surface layer portion in Table 4 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
No.28之本發明例，內層5含有工業用純鈦JIS1種，表層3、4含有Si，其厚度為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 28, the inner layer 5 contains one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.29之本發明例，內層5含有工業用純鈦JIS2種，表層3、4含有Si，其厚度為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 29, the inner layer 5 contains two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, and the thickness thereof is 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，作為扁胚6，使用進行電子射束熔解並以角型鑄模鑄造後，當作輥軋面之面經切削精整的厚度220mm×寬度1000mm×長度4500mm之錠。 Specifically, as the flat embryo 6, an ingot having a thickness of 220 mm × a width of 1000 mm × a length of 4,500 mm which is subjected to cutting and finishing as a surface of a rolled surface is used after being subjected to electron beam melting and casting by an angle casting.
作為鈦合金板7，表5之No.30中係將含有Ti-1.0Cu-1.0Sn-0.45Si-0.2Nb之鈦合金板，No.31中係將含有Ti-1.0Cu-0.5Nb之鈦合金板，No.32中係將含有Ti- 0.25Fe-0.45Si之鈦合金板，No.33中係將含有Ti-0.35Fe-0.45Si之鈦合金板，分別在真空中熔接於扁胚6的表面上。 As the titanium alloy sheet 7, No. 30 in Table 5 will contain Ti-1.0Cu-1.0Sn-0.45Si-0.2Nb titanium alloy sheet, and No. 31 will contain Ti-1.0Cu-0.5Nb titanium. Alloy plate, No.32 will contain Ti- A titanium alloy plate of 0.25Fe-0.45Si, No. 33, was a titanium alloy plate containing Ti-0.35Fe-0.45Si, which was welded to the surface of the flat embryo 6 in a vacuum.
而後，將該扁胚加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後進行冷軋，而形成厚度1mm之鈦板，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理，製造表5所示之No.30~33的本發明例之供試驗材即鈦複合材2。 Then, the slab was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using blasting and nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment is performed by heating to 600 to 700 ° C in a vacuum or an inert gas atmosphere for 240 minutes, and No. 30 to 33 shown in Table 5 is produced. The titanium composite material 2, which is a test material of the present invention.
針對此等供試驗材，與實施例1相同地，求得每個單位截面積之氧化增量。結果一併示於表5中。又，表5中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 With respect to these test materials, the oxidation increment per unit cross-sectional area was determined in the same manner as in Example 1. The results are shown together in Table 5. Further, the elemental concentrations in the surface layer portion in Table 5 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
No.30~33之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Si、Nb、Ta、Al之一種以上，其厚度為5μm以上，具有充分之厚度。另外，雖含有其他合金但其含量小於2.5%。再者，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 30 to 33, the inner layer 5 is of industrial pure titanium JIS, and the surface layers 3 and 4 contain one or more of Si, Nb, Ta, and Al, and have a thickness of 5 μm or more and a sufficient thickness. In addition, although it contains other alloys, its content is less than 2.5%. Further, the oxidation increment under heating for 200 hours at 700 ° C was 25 g/m 2 or less, and the oxidation increment under heating at 750 ° C for 200 hours was 70 g/m 2 or less, showing excellent oxidation resistance.
將第2圖所示之鈦複合材2利用以下之程序製造。 The titanium composite 2 shown in Fig. 2 was produced by the following procedure.
具體言之，作為扁胚6，係使用進行電子射束熔解並以角型鑄模鑄造後，將當作輥軋面之面切削精整成之厚度200mm×寬度1000mm×長度4500mm的鈦合金錠。 Specifically, as the flat embryo 6, a titanium alloy ingot having a thickness of 200 mm × a width of 1000 mm × a length of 4,500 mm was cut and formed into a surface of a rolled surface by electron beam melting and casting by an angle casting.
表6之No.34中係於含有Ti-1.0Cu-1.0Sn之扁胚6的表面上，No.35中係於含有Ti-1.0Cu-1.0Sn之扁胚6的表面上，No.36中係於含有Ti-0.5Al之扁胚6的表面上，No.37中係於含有Ti-0.9Al之扁胚6的表面上，No.38中係於含有Ti-3Al-2.5V之扁胚6的表面上，No.39中係於含有Ti-1Fe-0.35O之扁胚6的表面上，No.40中係於含有Ti-1.5Fe-0.5O之扁胚6的表面上，No.41中係於含 有Ti-0.5Cu之扁胚6的表面上，No.42中係於含有Ti-5Al-1Fe之扁胚6的表面上，No.43中係於含有Ti-6Al-4V之扁胚6的表面上，No.44中係於含有Ti-20V-4Al-1Sn之扁胚6的表面上，No.45中係於含有Ti-15V-3Al-3Cr-3Sn之扁胚6的表面上，分別於真空中熔接含有Si、Nb、Ta、Al中之一種以上的鈦板7。而後，將該扁胚加熱至950℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後於No.34~41中進一步進行冷軋，而形成厚度1mm之鈦板，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理，製造表6所示之No.34~41的本發明例之供試驗材即鈦複合材2。又，進而於No.42~45中於去皮膜處理後，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理，製造表6所示之No.42~45的本發明例之供試驗材即鈦複合材2。 No. 34 in Table 6 is on the surface of the flat embryo 6 containing Ti-1.0Cu-1.0Sn, and No. 35 is on the surface of the flat embryo 6 containing Ti-1.0Cu-1.0Sn, No. 36 The middle is on the surface of the flat embryo 6 containing Ti-0.5Al, the No. 37 is on the surface of the flat embryo 6 containing Ti-0.9Al, and the No. 38 is on the flat containing Ti-3Al-2.5V. On the surface of the embryo 6, No. 39 is attached to the surface of the flat embryo 6 containing Ti-1Fe-0.35O, and No. 40 is attached to the surface of the flat embryo 6 containing Ti-1.5Fe-0.5O, No. .41 in the system On the surface of the flat embryo 6 having Ti-0.5Cu, No. 42 is attached to the surface of the flat embryo 6 containing Ti-5Al-1Fe, and No. 43 is attached to the flat embryo 6 containing Ti-6Al-4V. On the surface, No. 44 is attached to the surface of the flat embryo 6 containing Ti-20V-4Al-1Sn, and No. 45 is attached to the surface of the flat embryo 6 containing Ti-15V-3Al-3Cr-3Sn. One or more titanium plates 7 containing Si, Nb, Ta, and Al are welded in a vacuum. Then, the slab was heated to 950 ° C, and hot rolled to a thickness of 5 mm, and then the surface of the front and back were subjected to a peeling treatment by sand blasting and nitric acid. Then, cold rolling is further carried out in No. 34 to 41 to form a titanium plate having a thickness of 1 mm, and as an annealing treatment, heat treatment is carried out in a vacuum or an inert gas atmosphere to 600 to 700 ° C for 240 minutes, and the heat treatment is performed. The titanium composite material 2 which is a test material of the present invention example shown in No. 34 to 41 is shown. Further, after the debarking treatment in Nos. 42 to 45, the annealing treatment is carried out by heating in a vacuum or an inert gas atmosphere to 600 to 700 ° C for 240 minutes, and the No. 6 shown in Table 6 is produced. The titanium composite material 2 which is a test material of the present invention of 42 to 45 is used.
針對此等供試驗材，與實施例1相同地，求得每個單位截面積之氧化增量。結果一併示於表6中。又，表6中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 With respect to these test materials, the oxidation increment per unit cross-sectional area was determined in the same manner as in Example 1. The results are shown together in Table 6. Further, the elemental concentrations in the surface layer portion in Table 6 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
No.34~45之本發明例，均為表層3、4含有Si、Nb、Ta、Al之一種以上，其厚度為5μm以上，具有充分之厚度。再者，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the examples of the invention of Nos. 34 to 45, each of the surface layers 3 and 4 contains one or more of Si, Nb, Ta, and Al, and has a thickness of 5 μm or more and a sufficient thickness. Further, the oxidation increment under heating for 200 hours at 700 ° C was 25 g/m 2 or less, and the oxidation increment under heating at 750 ° C for 200 hours was 70 g/m 2 or less, showing excellent oxidation resistance.
熱軋用鈦素材，係使用進行電子射束熔解並以角型鑄模鑄造之厚度200mm×寬度1000mm×長度4500mm者。對於熱軋用鈦素材之表面，除散布含有Nb、Si、Ta、Al之一種以上的素材以外，又進行表層之熔融。然後，將熱軋用鈦素材之表面溫度以150℃之溫度保持1小時以上。而後，將該熱軋用鈦素材加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後進行冷軋，而形成厚度1.0mm之鈦板，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~750℃並保持240分鐘之熱處理，製造表7之No.46~66所示的參考例及本發明例之供試驗材。此等供試驗材之多數具有第1、2圖所示之鈦複合材1、2的構造。 The titanium material for hot rolling is a thickness of 200 mm × a width of 1000 mm × a length of 4,500 mm which is subjected to electron beam melting and cast by angle molding. The surface of the titanium material for hot rolling is melted in addition to one or more materials containing Nb, Si, Ta, and Al. Then, the surface temperature of the titanium material for hot rolling was maintained at a temperature of 150 ° C for 1 hour or more. Then, the titanium material for hot rolling was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then the surface of the front and back surfaces were subjected to a peeling treatment by sand blasting and nitric acid. Then, cold rolling is performed to form a titanium plate having a thickness of 1.0 mm, and as an annealing treatment, heat treatment is carried out in a vacuum or an inert gas atmosphere to 600 to 750 ° C for 240 minutes, and No. 46 to 66 of Table 7 is produced. The reference examples shown and the test materials of the examples of the present invention. Most of these test materials have the structures of the titanium composites 1 and 2 shown in Figs.
自此等供試驗材切出20mm×20mm之試驗 片，將其表面與端部以# 400之砂紙研磨後，於700℃、750℃之各溫度下於大氣中曝露200小時，測定試驗前後之重量之變化，求得每個單位截面積之氧化增量。結果彙總示於表7中。又，表7中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 Test for cutting 20mm × 20mm from the test material The sheet was ground with a #400 sandpaper, and exposed to the atmosphere at 700 ° C and 750 ° C for 200 hours. The change in weight before and after the test was measured to determine the oxidation per unit cross-sectional area. Incremental. The results are summarized in Table 7. Further, the elemental concentrations in the surface layer portion in Table 7 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
又，表層部中雖含有由來自扁胚(母材)之元素，但表中僅表示不含於扁胚中之元素的含量。 Further, the surface layer portion contains an element derived from a flat embryo (base material), but the content of the element contained in the flat embryo is only indicated in the table.
No.46之比較例，內層5為工業用純鈦JIS2種，不具有表層3、4。因此，700℃之200小時的加熱下之氧化增量為40g/m2以上，750℃之200小時的加熱下之氧化增量為100g/m2以上，非常之高。 In the comparative example of No. 46, the inner layer 5 was of industrial pure titanium JIS, and did not have the surface layers 3 and 4. Therefore, the oxidation increase under heating at 700 ° C for 200 hours is 40 g/m 2 or more, and the increase in oxidation under heating at 750 ° C for 200 hours is 100 g/m 2 or more, which is extremely high.
No.47之比較例，內層5為工業用純鈦JIS2種，表層3、4含有Si，但其厚度為1μm非常之薄。因此，700℃之200小時的加熱下之氧化增量為40g/m2以上，750℃之200小時的加熱下之氧化增量為100g/m2以上，非常之高。 In the comparative example of No. 47, the inner layer 5 was industrial pure titanium JIS, and the surface layers 3 and 4 contained Si, but the thickness thereof was very thin at 1 μm. Therefore, the oxidation increase under heating at 700 ° C for 200 hours is 40 g/m 2 or more, and the increase in oxidation under heating at 750 ° C for 200 hours is 100 g/m 2 or more, which is extremely high.
No.48之本發明例，內層5為工業用純鈦JIS1種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 48, the inner layer 5 is one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.49之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 49, the inner layer 5 is of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.50之本發明例，內層5為工業用純鈦JIS3種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 50, the inner layer 5 is three kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.51之本發明例，內層5為工業用純鈦JIS4種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70 g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 51, the inner layer 5 is four kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Therefore, the oxidation increase under heating for 200 hours at 700 ° C is 25 g / m 2 or less, and the increase in oxidation under heating at 750 ° C for 200 hours is 70 g / m 2 or less, showing excellent oxidation resistance.
No.52之比較例，內層5為工業用純鈦JIS2種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度，然Si含量高至0.7%。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性，但在熱軋及冷軋時發生破裂，加工性劣化。 In the comparative example of No. 52, the inner layer 5 is industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness, and the Si content is as high as 0.7%. Therefore, the oxidation increase under heating for 200 hours at 700 ° C is 25 g / m 2 or less, and the increase in oxidation under heating at 750 ° C for 200 hours is 70 g / m 2 or less, showing excellent oxidation resistance, but in heat Cracking occurs during rolling and cold rolling, and workability is deteriorated.
No.53~66之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Si、Nb、Ta、Al之一種以上，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 53 to 66, the inner layer 5 is two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain one or more of Si, Nb, Ta, and Al, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.67~69所示之本發明例，熱軋用鈦素材係使用進行電子射束熔解並以角型鑄模鑄造後，將當作輥軋面之面切削精整而成之厚度100mm×寬度1000mm×長度4500mm者。於熱軋用鈦素材散布含有Nb、Si、Al之一種以上之素材後，進行表層熔融，而後以300℃之溫度保持1小時以上。 In the example of the present invention shown in No. 67 to 69, the titanium material for hot rolling is subjected to electron beam melting and cast by angle molding, and then cut into a roll surface to have a thickness of 100 mm × width. 1000mm × length 4500mm. After dissolving one or more materials containing Nb, Si, and Al in the titanium material for hot rolling, the surface layer is melted, and then held at a temperature of 300 ° C for 1 hour or longer.
而後，將該扁胚加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後進行冷軋，而形成厚度1.0mm之鈦板，作為 退火處理，係進行於真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理，製造表8所示之No.67~69的本發明例之鈦複合材2。 Then, the slab was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using blasting and nitric acid. Then cold rolling is performed to form a titanium plate having a thickness of 1.0 mm as The annealing treatment was carried out by heating to 600 to 700 ° C in a vacuum or an inert gas atmosphere for 240 minutes, and the titanium composite material 2 of the present invention shown in Table 8 of No. 67 to 69 was produced.
自此等供試驗材切出20mm×20mm之試驗片，將其表面與端部以# 400之砂紙研磨後，於700℃、750℃之各溫度下於大氣中曝露200小時，測定試驗前後之重量之變化，求得每個單位截面積之氧化增量。結果彙總示於表8中。又，表8中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 From this, the test piece of 20 mm × 20 mm was cut out from the test material, and the surface and the end portion were ground with #400 sandpaper, and then exposed to the atmosphere at 700 ° C and 750 ° C for 200 hours, before and after the test. The change in weight is used to determine the oxidation increment per unit cross-sectional area. The results are summarized in Table 8. Further, the elemental concentrations in the surface layer portion in Table 8 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
又，表層部中雖含有由來自扁胚(母材)之元素，但表中僅表示不含於扁胚中之元素的含量。 Further, the surface layer portion contains an element derived from a flat embryo (base material), but the content of the element contained in the flat embryo is only indicated in the table.
No.67之本發明例，內層5為工業用純鈦JIS1種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 67, the inner layer 5 is one type of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.68之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Nb，其厚度也為5μm以上，具有充 分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 68, the inner layer 5 is of industrial pure titanium JIS, and the surface layers 3 and 4 contain Nb, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.69之本發明例，內層5為工業用純鈦JIS3種，表層3、4含有Si及Al，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 69, the inner layer 5 is three kinds of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si and Al, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
表9之No.70~72所示之本發明例之中，熱軋用鈦素材係使用進行電漿熔解，並以角型鑄模鑄造之厚度200mm×寬度1000mm×長度4500mm者。對於熱軋用鈦素材散布含有Nb、Si、Al之一種以上的素材後，進行表層熔融之後，將素材表面溫度以300℃之溫度保持1小時以上。又，No.27所示之本發明例中，熱軋用鈦素材係使用進行電漿熔解，並以角型鑄模鑄造後，將當作輥軋面之面切削精整而成之厚度200mm×寬度1000mm×長度4500mm者。於熱軋用鈦素材散布含有Nb、Si、Al之一種以上的素材後，進行表層熔融，而後將素材表面溫度以250度之溫度保持1小時以上。 In the examples of the present invention shown in Nos. 70 to 72 of Table 9, the titanium material for hot rolling was subjected to plasma melting, and was cast by angle casting to have a thickness of 200 mm × a width of 1000 mm × a length of 4,500 mm. After one or more materials containing Nb, Si, and Al are dispersed in the titanium material for hot rolling, the surface layer is melted, and then the surface temperature of the material is maintained at a temperature of 300 ° C for 1 hour or more. Further, in the example of the invention shown in No. 27, the titanium material for hot rolling is subjected to plasma melting, and is cast by an angle mold, and the thickness of the surface to be rolled is 200 mm × The width is 1000mm × the length is 4500mm. After the material containing one or more of Nb, Si, and Al is dispersed in the titanium material for hot rolling, the surface layer is melted, and then the surface temperature of the material is maintained at a temperature of 250 degrees for 1 hour or longer.
而後，將該扁胚加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後，作為退火處理，係進行於真空或惰性氣體氛 圍中加熱至600~700℃並保持240分鐘之熱處理。 Then, the slab was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using blasting and nitric acid. Then, as an annealing treatment, it is carried out in a vacuum or an inert gas atmosphere. Heat it to 600~700 °C and keep it for 240 minutes.
自此等供試驗材切出20mm×20mm之試驗片，將其表面與端部以# 400之砂紙研磨後，於700℃、750℃之各溫度下於大氣中曝露200小時，測定試驗前後之重量之變化，求得每個單位截面積之氧化增量。結果彙總示於表9中。又，表9中之表層部之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 From this, the test piece of 20 mm × 20 mm was cut out from the test material, and the surface and the end portion were ground with #400 sandpaper, and then exposed to the atmosphere at 700 ° C and 750 ° C for 200 hours, before and after the test. The change in weight is used to determine the oxidation increment per unit cross-sectional area. The results are summarized in Table 9. Further, the elemental concentrations in the surface layer portion in Table 9 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
又，表層部中雖含有由來自扁胚(母材)之元素，但表中僅表示不含於扁胚中之元素的含量。 Further, the surface layer portion contains an element derived from a flat embryo (base material), but the content of the element contained in the flat embryo is only indicated in the table.
No.70之本發明例，內層5為工業用純鈦JIS1種，表層3、4含有Si，再者，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 70, the inner layer 5 is one type of industrial pure titanium JIS, the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.71之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Nb，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為 70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 71, the inner layer 5 is of industrial pure titanium JIS, and the surface layers 3 and 4 contain Nb, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.72之本發明例，內層5為工業用純鈦JIS3種，表層3、4含有Si及Al，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 72, the inner layer 5 is three kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si and Al, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
表10中所記載之No.73所示之本發明例之中，熱軋用鈦素材係採用藉由分解形成為矩形形狀後，將當作輥軋面之面切削精整而成之厚度200mm×寬度1000mm×長度4500mm者。於熱軋用鈦素材散布含有包含Si之各元素的素材後，進行表層熔融，而後將熱軋用鈦素材之表面溫度以150℃之溫度保持1小時以上。又，No.74所示之本發明例之中，熱軋用鈦素材係使用藉由分解而形成為矩形形狀後，將當作輥軋面之面切削精整而成之厚度50mm×寬度1000mm×長度4500mm者。於熱軋用鈦素材散布含有包含Si之各元素的素材後，進行表層熔融，而後將熱軋用鈦素材之表面溫度以350℃之溫度保持1小時以上。 In the example of the invention shown in No. 73 described in Table 10, the titanium material for hot rolling is formed into a rectangular shape by decomposition, and the thickness of the surface to be rolled is 200 mm. × width 1000mm × length 4500mm. After the material containing each element of Si is dispersed in the titanium material for hot rolling, the surface layer is melted, and then the surface temperature of the titanium material for hot rolling is maintained at a temperature of 150 ° C for 1 hour or more. Further, in the example of the invention shown in No. 74, the titanium material for hot rolling is formed into a rectangular shape by decomposition, and the thickness of the surface to be rolled is 50 mm × width 1000 mm. × Length 4500mm. After the material containing each element of Si is dispersed in the titanium material for hot rolling, the surface layer is melted, and then the surface temperature of the titanium material for hot rolling is maintained at a temperature of 350 ° C for 1 hour or more.
而後，將該扁胚加熱至820℃，並熱軋至厚度5mm後，利用噴砂及硝氟酸，針對表背面均進行去皮膜處理。然後，作為退火處理，係進行於真空或惰性氣體氛圍中加熱至600~700℃並保持240分鐘之熱處理。 Then, the slab was heated to 820 ° C, and hot rolled to a thickness of 5 mm, and then subjected to a peening treatment using blasting and nitric acid. Then, as an annealing treatment, heat treatment is carried out by heating to 600 to 700 ° C in a vacuum or an inert gas atmosphere for 240 minutes.
自此等供試驗材切出20mm×20mm之試驗片，將其表面與端部以# 400之砂紙研磨後，於700℃、750℃之各溫度下於大氣中曝露200小時，測定試驗前後之重量之變化，求得每個單位截面積之氧化增量。結果彙總示於表10中。又，表10中之表層3、4之元素濃度，係利用EPMA進行線性分析，將自表面以至合金層之下端的範圍平均之結果。 From this, the test piece of 20 mm × 20 mm was cut out from the test material, and the surface and the end portion were ground with #400 sandpaper, and then exposed to the atmosphere at 700 ° C and 750 ° C for 200 hours, before and after the test. The change in weight is used to determine the oxidation increment per unit cross-sectional area. The results are summarized in Table 10. Further, the elemental concentrations of the surface layers 3 and 4 in Table 10 were linearly analyzed by EPMA, and the results from the surface to the lower end of the alloy layer were averaged.
又，表層部中雖含有由來自扁胚(母材)之元素，但表中僅表示不含於扁胚中之元素的含量。 Further, the surface layer portion contains an element derived from a flat embryo (base material), but the content of the element contained in the flat embryo is only indicated in the table.
No.73之本發明例，內層5為工業用純鈦JIS1種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 73, the inner layer 5 is one type of industrial pure titanium JIS, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
No.74之本發明例，內層5為工業用純鈦JIS2種，表層3、4含有Si，其厚度也為5μm以上，具有充分之厚度。因此，700℃之200小時的加熱下之氧化增量為25g/m2以下，750℃之200小時的加熱下之氧化增量為70g/m2以下，顯示優異之耐氧化性。 In the example of the invention of No. 74, the inner layer 5 is two kinds of pure titanium JIS for industrial use, and the surface layers 3 and 4 contain Si, and the thickness thereof is also 5 μm or more, and has a sufficient thickness. Thus, the oxidized amount of 700 deg.] C for 200 hours of heating was 25g / m 2 or less, the increase of oxidation for 200 hours at 750 deg.] C the heating was 70g / m 2 or less, it exhibits excellent oxidation resistance.
1‧‧‧鈦複合材 1‧‧‧Titanium composite
3‧‧‧表層 3‧‧‧ surface layer
5‧‧‧內層 5‧‧‧ inner layer
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|---|---|---|---|---|
| US5579988A (en) * | 1995-06-09 | 1996-12-03 | Rmi Titanium Company | Clad reactive metal plate product and process for producing the same |
| JP3296271B2 (en) * | 1997-02-14 | 2002-06-24 | 日本鋼管株式会社 | Titanium clad steel sheet and its manufacturing method |
| JP4398666B2 (en) * | 2002-05-31 | 2010-01-13 | 新日本製鐵株式会社 | Unidirectional electrical steel sheet with excellent magnetic properties and method for producing the same |
| JP4516440B2 (en) * | 2004-03-12 | 2010-08-04 | 株式会社神戸製鋼所 | Titanium alloy with excellent high-temperature oxidation resistance and corrosion resistance |
| JP2011174120A (en) * | 2010-02-23 | 2011-09-08 | Thk Co Ltd | Titanium material, rolling device including component composed of titanium material, and method for producing the titanium material |
| JP2016128172A (en) * | 2013-04-01 | 2016-07-14 | 新日鐵住金株式会社 | Titanium hot rolling ingot being hard to cause surface flaw and its manufacturing method |
| JP2016128171A (en) * | 2013-04-01 | 2016-07-14 | 新日鐵住金株式会社 | Titanium hot rolling slab being hard to cause surface flaw and its manufacturing method |
-
2016
- 2016-07-29 TW TW105124190A patent/TWI632959B/en not_active IP Right Cessation
- 2016-07-29 JP JP2017530940A patent/JP6515359B2/en active Active
- 2016-07-29 WO PCT/JP2016/072336 patent/WO2017018514A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017018514A1 (en) | 2017-02-02 |
| TWI632959B (en) | 2018-08-21 |
| JPWO2017018514A1 (en) | 2018-05-24 |
| JP6515359B2 (en) | 2019-05-22 |
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